New types of electrodeposited polymer coatings with reversible wettability and electro-optical properties

ABSTRACT

Novel coatings are disclosed prepared by electropolymerization of non-fluorinated conducting pre-grafted hydrophobic electropolymerizable monomers onto a conducting layer of a substrate, where the electropolymerized coating exhibit both unique reversible wettability and electro-optical properties. The coating may also include one or more layers of polymer particles upon which the non-fluorinated conducting pre-grafted hydrophobic electropolymerizable monomers are polymerized imparting a submicron structure to the coating. Methods for making and using the coatings are also disclosed.

RELATED APPLICATIONS

This application is a divisional of U.S. patent application Ser. No.13/179,515 filed Jul. 9, 2011 (9 Jul. 2011) now U.S. Pat. No. 9,248,467issued Feb. 2, 2016 (2 Feb. 2016), which claims the benefit of andpriority to U.S. Provisional Patent Application Ser. No. 61/363,696filed 13 Jul. 2010 (07/13/2010)(13.07.2010).

GOVERNMENTAL SPONSORSHIP

Embodiments of the inventions set forth herein were in part funded byNSF CBET-0854979, and DMR-10-06776 and governmental rights may attach tothese embodiments or portions thereof.

REFERENCE TO A SEQUENTIAL LISTING

Not Applicable.

BACKGROUND OF THE INVENTION

1. Field of the Invention

Embodiments of the present invention relates to designs, fabrications,characterizations, and uses of new types of electrodeposited polymercoatings that offer both unique reversible wettability andelectro-optical properties.

More specifically, embodiments of the invention enable the formation ofsuperhydrophobic and superlipophilic conducting surfaces made fromnon-fluorinated conducting polymers. Such surfaces are built following atwo-step approach, which is capable of being applied to a variety ofmaterials. The precursor reagents or agents include non-fluorinatedconducting polymers of pre-grafted hydrophobic chains that are firstelectrodeposited by anodic electropolymerization or chemical oxidativemethods onto layers of polymer particles such as polystyrene particlespre-assembled on an electrode surface such as a gold (Au) surface. Thelayering of the particles such as latex microspheres provides thesubmicron size roughness of a biomimetic surface imitating a geometricalmicrostructure of a surface of a lotus leaf for example. The overallcoatings described herein exhibit both tunable electrochromic andwettability properties that are tuned by applying an electric potentialacross the surface. Electro-optical properties may be controlled basedon a level of doping and type of chemical structures utilized. Moreover,the use of surfactants on top of such coatings allows one to furthertune the wettability behavior. While this work emphasizes the use ofconducting polymers by anodic polymerization, the design may be extendedto non-conducting polymers such as acrylate, styrene, vinyl functionalgroups using cathodic electropolymerization or chemical reductivemethods instead of anodic electropolymerization. Also, the coating canbe done on a variety of metallic, metal alloy, metal-oxide andnon-metallic substrates of various size, shape, and geometry, providedthe requirements for deposition of particles and polymers can beaccomplished. Important applications of such coatings may be in the formof anti-wetting, filtration, anti-corrosion, de-icing, anti-microbial,electrochromic, and electrophoretic or electro-wetting applications,where the wetting properties of the film play an important role.

2. Description of the Related Art

The water-repellent behavior of a lotus leaf is a wonder of nature thatmarvels many scientists of diverse backgrounds. A lotus leaf will give awater contact angle greater than 150° with only 2-3% of the water dropto come into contact with its leaf, and is therefore considered asuperhydrophobic surface. This property is attributed to the synergisticeffect of two important factors such as (1) hierarchical roughness,which are the nanometer scale asperities within the micron scalegeometrical structures and (2) low surface energy wax epicuticula on thesurface of the leaf. Its high water resistance property is well worthmimicking because of the many industrial and practical applicationsnamely self-cleaning, anti-fouling marine coatings, stain-resistantfabrics, oxidation resistant surfaces, anti-adhesive coatings,nano-battery, microfluidics, anti-biofouling, etc.

With the basic understanding of the natural design of a lotus leaf, anartificial superhydrophobic surface can be accomplished by developing adual-scale roughness structure and tuning the surface energy of thesurface. Recently, electrically conducting polymers with fluorinatedfunctional group has been used extensively to make a surface that wouldconfer water and also oil resistance. Conducting polymers have been alsoused to develop various types of industrial coatings for anti-corrosionand anti-static purposes. Furthermore, conducting polymers have uniqueelectro-optical properties making them useful for display materials,semi-conductors, electrochromic devices, fluorescent materials,non-linear optical materials, electromagnetic shielding, etc.

Unlike the other methods of creating polymer coatings such aselectrospinning, lithography, and layer-by-layer assembly, theelectrochemical deposition offers the following advantages likeinexpensive, fast and easy to use. It has been used on a variety ofelectrode surfaces mostly based on metal or semi-conductor andtransparent substrates such as Au, Ag, Al, stainless steel, indium tinoxide (ITO), etc. This includes similarly, the vertical depositionmethod also called the Langmuir-Blodgett (LB) like-technique used forthe layering of polystyrene particles on conducting surface, which doesnot necessarily require a sophisticated technology.

Thus, there is a need in the art for new efficient and cost effectivetechniques for making a highly-ordered and closely packed arrays of thelatex microspheres on flat surfaces having unique electrochromic andwettability properties.

SUMMARY OF THE INVENTION

Embodiments of the present invention provide electrochemical depositionmethods for the design, use, and fabrication of unique coatings thatexhibits both electrochromic and extreme wettability properties such assuperhydrophobicity and superhydrophilicity. Such electro-opticalproperties may be tunable, tailored and/or altered by applying apotential and by varying the chemical structure and composition of thepolymers, which may further be modified by treating the coating with asurfactant. Certain embodiments of this invention provide compositionsusing conducting polymers prepared by anodic polymerization or chemicaloxidative polymerization. While the present invention emphasizes the useof conducting polymers by anodic polymerization, it is possible toextend the proposed design to non-conducting polymers such as, but notlimited to acrylate, styrene, or vinyl functional monomer groups viacathodic electropolymerization or chemical reductive polymerization,involving radical or anion mechanisms. That is, electropolymerizabilitycan be in the form of radical cation or radical anion generation. Theelectrochemical methods may be done using various shapes, sizes, andgeometries of the electrode and may include a choice betweenpotentiodynamic and potentiostatic or chronoamperometric and pulsedmethods and other variants involving chemical redox methods. Otherelectrode or solid support substrates include noble metals, steel,stainless steel, metal alloys, metal oxides, graphite or carbonelectrode surfaces, transparent electrodes, plastic surfaces, and othersurfaces capable of colloidal templating and deposition orpolymerization of monomers of the same or analogous procedure. Yet otherembodiments provide the use of colloidal templated features onto thesubstrate where colloidal templating can be done using polymeric,non-polymeric, inorganic, metal oxide, and other synthetic colloidalparticles. This can include polystyrene, polymethylmethacrylate,polyamides, phenolic resins, silica, silicon oxide, titanium oxide, andother synthetic colloidal particles.

Embodiments of the present invention provide anodic electropolymerizablemonomers of the general formula (I):

A-RZ  (I)

where A is an anodic electropolymerizable group, where A is selectedfrom the group consisting of an A_(p) or L(A_(p))_(n), where L is alinking group and the R group of is bonded to L and n is an integerhaving a value between 1 and 4, R is alkenyl group having between 1 andabout 20 carbon atoms, where one or more of the carbon atoms may bereplaced by oxygen atoms, amino groups, amide groups, ester groups, ormixtures thereof, and Z is an end group selected from the groupconsisting of OH, COOH, COOR¹, NR²R³, CONR⁴R⁵, A¹OH, A¹COOH, A¹COOR¹,A¹NR²R³, A¹CONR⁴R⁵, and mixtures thereof, where R¹⁻⁵ are carbyl grouphaving between 1 and about 10 carbon atoms. In certain embodiments, thecompounds of formula (I) are simply A_(p)-RZ. In other embodiments, thecompounds of formula (I) are simply (A_(p))_(n)L-RZ.

Embodiments of the present invention provide cathodicelectropolymerizable monomers including ethylenically unsaturatedmonomers, diene monomers or mixtures or combinations thereof, where themonomers are polymerized through radical or radical anion generationwith cathodic polymerization or chemical reductive polymerization, acomplement to anodic electropolymerization.

BRIEF DESCRIPTION OF THE DRAWINGS

The invention can be better understood with reference to the followingdetailed description together with the appended illustrative drawings inwhich like elements are numbered the same:

Drawing of Section I

FIG. 1 depicts synthetic Scheme 2 illustrating the method of fabricationto create surface coatings that are superhydrophobic andsuperliphophilic and conducting.

FIGS. 2A-D depict CV diagrams (monomer free scan on inset) of theeletropolymerization of monomers: (1) G0-3TCOOR (5 mM) onto (A) PScoated Au and (B) bare Au and (2) G0-3TCOOH (5 mM) onto (C) PS coated Auand (D) bare Au.

FIGS. 3A-I depict static contact angle measurements in water of (A) PS(500 nm size)-coated Au/BK 7, (B) poly(G0-3TCOOR) on Au/BK 7, (C)poly(G0-3TCOOR) on PS (100 nm size)-coated Au/BK 7, (D) poly(G0-3TCOOR)on PS (500 nm size)-coated Au/BK 7, (E) poly(G0-3TCOOH) on Au/BK 7, (F)poly(G0-3TCOOH) on PS (100 nm size)-coated Au/BK 7, (G) poly(G0-3TCOOH)on PS (500 nm size)-coated Au/BK 7, in diiodomethane of (H)poly(G0-3TCOOR) on PS (500 nm size)-coated Au/BK 7, and in hexadecane of(I) poly(G0-3TCOOR) on PS (500 nm size)-coated Au/BK 7.

FIG. 4A-F depict surface morphology studies: AFM micrograph (A) 2D and(B) 3D of PS (500 nm size)-coated Au/BK 7 and SEM micrographs (C), (E)low and (D), (F) high magnification of poly(G0-3TCOOR) on PS-coatedAu/BK 7, and poly(G0-3TCOOR) on bare Au/BK 7, respectively.

FIG. 5 depict ATR IR spectra of (red) poly(G0-3TCOOR) on 500 nm size PSAu, (black) poly(G0-3TCOOR) on bare Au, (green) poly(G0-3TCOOH) on 500nm size PS Au, (blue) poly(G0-3TCOOH) on bare Au, and (gray) 500 nm sizePS coated Au (control film).

FIGS. 6A&B depicts static contact angle measurements of theelectropolymerized G0-3TCOOR onto PS (500 nm size) coated Au using waterat different temperatures.

FIG. 7 depicts static water contact angle measurements of theelectropolymerized G0-3TCOOR onto PS (500 nm size) coated Au to studyits long term stability in dry and ambient conditions.

FIG. 8 depicts static water contact angle measurements of theelectropolymerized G0-3TCOOR onto PS (500 nm size) coated Au as comparedto the other electropolymerized surfaces, prepared by electrodepositionof commercially available monomers onto 500 nm size PS coated Au.

FIGS. 9A-C depict reversible wettability and electrochromic properties:(A) Left and (B) right water contact angle at 0 V and 1.05 V of thepoly(G0-3TCOOR) on PS (500 nm size) coated-Au and poly(G0-3TCOOR) onbare Au as control. (C) Water contact angle and their photo images ofthe electropolymerized films, poly(G0-3TCOOR) on PS (500 nm size)coated-Au and poly(G0-3TCOOR) on bare Au at 0 V and 1.05 V.

FIGS. 10A&B depict (A) UV-Vis spectrum of poly(G0-3TCOOR) on bare ITO;(B) Photo images of poly(G0-3TCOOR) on bare ITO as it undergoes dedopingand doping for 2 cycles.

FIGS. 11A-E depict applications of constant potential (0 V or 1.05 V) bychronoamperommetric measurements to poly(G0-3TCOOR) on PS (500 nm size)coated Au (A) and bare Au (B).

FIG. 12 depict an XPS survey scans of the poly(G0-3TCOOR) on PS (500 nmsize) coated Au at 0 V (dedoped state) and 1.05 V (doped state).

FIGS. 13A-F depict XPS high resolution scans of the poly(G0-3TCOOR) onPS (500 nm size) coated Au at 0V and 1.05 V: (A) F 1s, (B) P 2p, (C) S2p, (D) Au 4f, (E) C 1s, and (F)O 1s.

FIG. 14 depicts contact angle measurements proving the conversion of thesuperhydrophobic and superlipophilic conducting surface(poly(G0-3TCOOR/PS (500 nm) Au)) into superhydrophilic and lipophobicconducting surface by one simple step, spincoating of fluorinatedsurfactants (S 760P).

Drawing of Section II

FIGS. 15A-H depict (A) Two-step process towards the formation ofsuperhydrophobic-and-superoleophilic conducting polymer nanostructuredsurface. AFM topography 2D images (3D on inset) of LB-like surfacelayering of PS nanoparticles: (B) 200 nm size, (C) 350 nm, and (d) 500nm. IR imaging showing (E) 2D and (F) 3D images with IR spectra focusedon (G) C—H stretch (area in dark gray or green) and (H) C═O stretch(area in light gray or cyan) regions. Note: Scanning area is 176×176μm².

FIGS. 16A&B depict CV diagrams (monomer free scan on inset) of theeletropolymerization of G0-3TCOOR monomer (5 mM concentration) onto (A)PS coated Au and (B) bare Au. Note: The mechanism of thiopheneelectropolymerization is found elsewhere.⁴

FIG. 17 ATR IR spectrum of (red) poly(G0-3TCOOR) on 500 nm size PS Au,(black) poly(G0-3TCOOR) on bare Au, (green) poly(G0-3TCOOH) on 500 nmsize PS Au, (blue) poly(G0-3TCOOH) on bare Au, and (gray) 500 nm size PScoated Au (control film). Note: Peaks were assigned based on publishedliteratures.^(5,6,7)

FIGS. 18A-G depict contact angle measurements of poly(G0-3TCOOR) onto500 nm PS/Au in (A) water, (B) diiodomethane, and (C) hexadecane. (D)Low 24×36 mm and (E) high magnification SEM images of poly(G0-3TCOOR)onto 500 nm PS/Au at 4×3 mm. Also a distinction between the: (F) Doped(1.05 V, 30 mins), and (G) dedoped (0 V, 30 mins) morphologies at widearea of 800×900 mm

FIGS. 19A-H depict morphology of the films at doped (left column) anddedoped (right column) states with increasing magnification (120× to20K×).

FIGS. 20A&B depict (A) Static water contact angle measurements of thesuperhydrophobic nanostructured film (poly(G0-3TCOOR) onto 500 nm PSlayer on Au) inclined at a very low sliding angle of 2°±1. (B) Lateralmovement at the surface of the superhydrophobic nanostructured film bythe water droplet hanging at the tip of the needle. Note: (1) click onthe first image to see the real time movie of the rolling of waterdroplet from the film. (2) The orange colored circle on the substrate isthe only area with the superhydrophobic coatings.

FIGS. 21A-I depict static contact angle measurements in water of (A) PS(500 nm size)-coated Au/BK 7, (B) poly(G0-3TCOOR) on Au/BK 7, (C)poly(G0-3TCOOR) on PS (100 nm size)-coated Au/BK 7, (D) poly(G0-3TCOOR)on PS (500 nm size)-coated Au/BK 7, (E) poly(G0-3TCOOH) on Au/BK 7, (F)poly(G0-3TCOOH) on PS (100 nm size)-coated Au/BK 7, (G) poly(G0-3TCOOH)on PS (500 nm size)-coated Au/BK 7, in diiodomethane of (H)poly(G0-3TCOOR) on PS (500 nm size)-coated Au/BK 7, and in hexadecane of(I) poly(G0-3TCOOR) on PS (500 nm size)-coated Au/BK 7.

FIGS. 22A&B Static water contact angle measurements of thesuperhydrophobic film (poly(G0-3TCOOR) onto 500 nm PS layer on Au) at(A) very high and (B) very low temperatures of water.

FIG. 23 depict stability studies showing static water contact anglemeasurements of the superhydrophobic film (poly(G0-3TCOOR) onto 500 nmPS layer on Au) and other films (commercially available monomerselectrodeposited atop 500 nm PS layer on Au). Note: Superhydrophobicfilm was fabricated onto 500 nm PS coated Au and 500 nm PS coated ITO.

FIGS. 24A-C depict static water contact angle of the poly(G0-3TCOOR)onto 500 nm PS layer on Au: (A) water, (B) diiodomethane, and (C)hexadecane.

FIGS. 25A-C depict reversible wettability and electro-opticalproperties: (A) Static water contact angle analysis of poly(G0-3TCOOR)on PS-templated Au (solid line) and poly(G0-3TCOOR) on bare Au (brokenline) via potential switching between 1.05V (doping) and 0V (dedoping)and (B) UV-Vis measurements of the doped (light gray orange coloredfilm) and dedoped (dark gray or dark green colored film) poly(G0-3TCOOR)electrodeposited on ITO. (C) XPS survey scans of the doped (broken linecurve) and dedoped (solid line curve) film. Note: The doping anddedoping of the films were carried out in ACN with the supportingelectrolyte (0.1 M TBAH) using the same electrochemistry set-up (FIG.15A) having three electrode system with the electrodeposited film on Auas the working electrode.

FIGS. 26A-F depict XPS high resolution scans of the poly(G0-3TCOOR) onto500 nm PS layer on Au at dedoped (superhydrophobic film, black curve)and doped (converted to hydrophilic film, red curve): (A) F 1s, (B) P2p, (C) S 2p, (D) Au 4f, (E) C 1s, and (F)O 1s. Note: Peaks wereassigned and compared with published literatures.^(8,9,10,11)

FIG. 27A-D depict contact angle measurements of poly(G0-3TCOOR) onto 500nm PS coated Au in (A) water before and after spin coating of S 760P in(B) water, (C) hexadecane, and (D) diiodomethane.

FIG. 28 depict an NMR spectrum of ethyl2-(2,5-dibromothiophen-3-yl)acetate.

FIG. 29 depict an NMR spectrum of ethyl2-(2,5-di(thiophen-2-yl)thiophen-3-yl)acetate (G0-3TCOOR).

FIG. 30 depict an NMR spectrum of2-(2,5-di(thiophen-2-yl)thiophen-3-yl)acetic acid (G0-3TCOOH).

FIG. 31 depict static contact angle measurements of the poly(G0-3TCOOR)onto 500 nm PS layer on Au and other control films before and after spincoating of fluorinated surfactants (S 760 P).

Drawing of Section III

FIGS. 32A&B depict (A) fabrication scheme of the superhydrophobicpolymeric surface by PS layering and CV (cyclicvoltammetry)-electropolymerization. (B) Protein (fibrinogen) andbacterial (E. coli) adhesion onto the undoped (orange-colored film) anddoped (green-colored film) colloidally-templated polythiophene(poly(G0-3TCOOR)/PS) surfaces.

FIGS. 33A-D depict AFM topography (A) 2D and (B) 3D images of the 500 nmsize PS coated-Au substrate with high magnification image on inset of(A). Note: AFM scan area is 6.5 μm×6.5 μm. SEM wide scan of the (C)doped and (D) undoped or dedoped colloidally-templated andelectrodeposited polythiophene surface (poly(G0-3TCOOR)/PS Au)). Insetshows the wetting behavior (contact angle) and the respective appliedvoltage.

FIGS. 34A-D depict AFM topography 2D images (3D on inset) of thedifferent sizes of PS assembled on Au: (A) 200 nm and (B) 350 nm. (C)500 nm PS assembled on ITO. (D) ATR IR spectrum of PS layer on Au.Notes: IR spectrum shows the signature peaks of PS: CH aromatic stretch(3083, 3061, 3026 cm⁻¹), CH aliphatic stretch (2990-2830 cm⁻¹), C═Caromatic stretch (1602 cm⁻¹), CH bending (1493, 1452 cm⁻¹), CH₂ rocking(1219 cm⁻¹), out of phase ring deformation (697 cm⁻¹).

FIGS. 35A&B depict (A) CV electrodeposition of the conducting polymer(poly(G0-3TCOOR)) with inset of the monomer-free post-polymerizationscan in 0.1 M TBAH/ACN. (B) XPS wide scan of the electropolymerized filmwith inset of the S 2p high resolution scan.

FIGS. 36A-D depicts (A) Digital photo image of the static water contactangle of the undoped poly(G0-3TCOOR) on PS coated Au. SEM images of theundoped polymeric surfaces: (B) hierarchical surface ordering, (C) highdense foam-like features, and (D) low area under layer (magnified imageof the under layer of (B)). Note: The red arrow indicates the low areaon the surface.

FIGS. 37A-D depict static water contact angle measurements of thesuperhydrophobic polymeric surface at (A) low and high temperatures andat (B) different pH values of water. (C) Digital photo images of theactual movement of the water droplet along the superhydrophobic surface.(D) Digital photo images of the superhydrophobic surface before(top-left, pristine) and after (bottom-left, dusted surface)self-cleaning studies (right) at sliding angle of 3°±1.

FIGS. 38A-C depict (A) UV-Vis spectrum and XPS high resolution peak of(B) fluorine and (C) phosphorus before and after doping of thepoly(G0-3TCOOR) film.

FIG. 39 depicts static water contact angle of the colloidally-templatedpolythiophene surface upon switching the potential of the conductingpolymer between 0 V (1, 3, 5) and 1.05 V (2, 4).

FIG. 40 depicts XPS high resolution scan of sulfur peak after doping anddedoping of the polythiophene.

FIG. 41 depicts a bar graph summary with inset of the in-situ bindingkinetic curve (average curve, n=3) of the QCM measurements of fibrinogenadsorption (1 mg/mL in PBS buffer, ˜950 minutes) on different surfaces:(1) poly(G0-3TCOOR)/PS Au undoped, (2) poly(G0-3TCOOR)/PS Au doped (1.05V, 30 mins), (3) bare Au, and (4) PBS injection to poly(G0-3TCOOR)/PS Auundoped (control film).

FIG. 42 depicts in-situ binding kinetic curve of the QCM measurements offibrinogen adsorption (1 mg/mL in PBS buffer, 950 minutes) on differentsurfaces: (1) poly(G0-3TCOOR)/PS Au undoped, (2) poly(G0-3TCOOR)/PS Audoped (1.05 V, 30 mins), (3) bare Au, (4) PBS injection topoly(G0-3TCOOR)/PS Au undoped (control film), and (5)poly(G0-3TCOOR)/bare Au.

FIGS. 43A-C depict static water contact angle and ATR IR measurements ofthe undoped (A) and doped (B) poly(G0-3TCOOR)/PS Au surface afterfibrinogen adsorption (1 mg/ml in PBS buffer, ˜950 minutes). (C) XPSwide scan of the doped (1.05 V) poly(G0-3TCOOR) before and afterfibrinogen adsorption with inset of N 1s high resolution scan.

FIGS. 44A-D depict bacterial adhesion during the 2 h incubation in E.coli solution and briefly washed by PBS buffer on the unit area ofdifferent surfaces (1 mm²×1 mm²) (A) Undoped poly(G0-3TCOOR)/PS Au, (B)doped (1.05 V) poly(G0-3TCOOR)/PS Au, and (C) bare ITO (control). (D)Bar graph summary of the statistical analysis of the bacterial celladhesion on the three surfaces. Notes: (1) values are averages withstandard deviations of at least 8 pictures conducted on a minimum of twoseparate experiments. (2) * denotes significant difference in terms ofthe bacterial adhesion compared to the unmodified control (p<0.05, ANOVAon ranks). (3) ** denotes significant difference in terms of thebacterial adhesion compared to the doped (p<0.05, ANOVA on ranks)

FIGS. 45A&B depicts NMR spectra of (A) ethyl2-(2,5-dibromothiophen-3-yl)acetate and (B) ethyl2-(2,5-di(thiophen-2-yl)thiophen-3-yl)acetate (G0-3TCOOR).

Drawing of Section IV

FIGS. 46A-H depict (A) Fabrication scheme of conducting polymer networkmonolayer array (inverse colloidal crystals) onto ITO substrate. Low (B,D, F) and high (C, E, G,) magnification AFM (in tapping mode) topography2D images (3D on inset) of (B), (C) colloidal crystals beforeelectropolymerization; (D), (E) colloidal crystals afterelectropolymerization; (F), (G) inverse colloidal crystals; and (H) SEM2D image of the inverse colloidal crystals.

FIG. 47A-G depict (A) Fabrication scheme of backfilling the insidecavities with silane SAM (ATRP-initiator) and polymer brush (PNIPAM).Low (B, E) and high (C, F) magnification AFM (in tapping mode)topography 2D images (3D on inset) of backfilled (B, C) Si—Br SAM and(E, F) pNIPAM brush. AFM line profile analysis of (D) Si—Br SAM and (G)pNIPAM brush versus bare ITO surface (before back filling).

FIGS. 48A&B depict (A) CV-electropolymerization of monomer (CBzTEGG1, 5mM conc) onto 500 nm PS layer. (B) Post polymerization scan or monomerfree scan of the electropolymerized film (poly(CBzTEGG1) atop the 500 nmPS layer.

FIGS. 49A&B depict In-situ EQCM monitoring of film deposition(poly(CBzTEGG1) onto 500 nm PS layer/Au QCM crystal. (A) cyclicvoltamogram and (B) QCM response.

FIGS. 50A-D depict XPS high resolution scans of the PS imprintedelectropolymerized film (after the removal of 500 nm size PS: C 1s (A),N 1s (B), O 1s (C), and Au 4f (D).

FIG. 51 depicts UV-Vis measurements of inverse opal (poly(CBzTEGG1)) onITO after the removal of 500 nm layer of PS. Note that the sample ismeasured directly in UV-Vis as a film.

FIG. 52 depicts 2D minimized structure of11-(2-Bromo-2-methyl)propionyloxy) undecyltrichlorosilane (ATRPinitiator) determined from Spartan (Spartan, Wavefunction Inc). Thetotal length and minimization energy of the molecule was calculatedusing Spartan and are equivalent to 18.6 angstrom and 99.7338 KJ/mole,respectively.

FIGS. 53A-C depict XPS and ATR IR measurements: (A) XPS high resolutionBr 3d scan of backfilled silane SAM onto inverse colloidal crystals, (B)XPS survey scan verifying the growth of pNIPAM brush onto the backfilledsilane initiator SAM on inverse colloidal crystal (on inset is Br 3dhigh resolution scan of the pNIPAM brush) and (C) ATR IR spectrum ofinverse colloidal crystals (poly(CBzTEGG1), dual pattern surface (pNIPAMbrush on inverse colloidal crystals), and pNIPAM brush on unpatternsurface (bare ITO).

FIGS. 54A-F depict CS-AFM (in contact mode) (A) topograpghy, (B)friction, (C) low and (D) high current images of the dual patternsurface on Au substrate: pNIPAM brush backfilling the holes of thepoly(CBzTEGG1) polymer array. I-V plot of (E) poly(CBzTEGG1) region and(F) pNIPAM brush region. Note: AFM scan area is 5 μm×5 μm.

DETAILED DESCRIPTION OF THE INVENTION

The inventors have found that novel coatings and surfaces incorporatingthe coatings can be constructed using electropolymerization anddeposition of polymers via electrochemical methods or chemical redoxpolymerization methods to form unique and novel coatings. Anotherfeature of this invention is the use of templating colloidal particlesdeposited on electrode surfaces that influence the morphology of theelectropolymerized outer layer. The coatings of this invention and thesurfaces incorporating them have unique structures and tunable,controllable and/or reversible wettability and electro-opticalproperties.

Suitable Reagents

Suitable anodic electropolymerizable or chemical oxidative polymerizableheterocylic aryl or aromatic group A_(p) for use in the presentinvention include, without limitation, single group compounds andmultigroup compounds. Exemplary single group compounds including,without limitation, pyrrole, thiophene, carbazole, indole, aniline,fluorene, and their fused heteroaromatic, oligomeric, and copolymericderivatives such as 2-(thiophen-2-yl)thiophene,2,5-di(thiophen-2-yl)thiophene, higher thiophene 2,5 oligomers, otheranodic electropolymerizable heterocylic aryl or aromatic groups andmixtures thereof. Exemplary multigroup compounds include compounds ofthe general formula (II):

L(R′A_(p))_(n)  (II)

where A_(p) is as set forth above and L is a linking group selected fromthe group an aromatic group, a dihydroxy aromatic group, a symmetricaldihydroxy substituted aromatic group, or mixtures thereof. Exemplarydiether substituted aromatic groups include, without limitation,methyl-3,5-dihydroxybenzoate, where the ester group is the RZ group.

Suitable ethylenically unsaturated monomers for cathodicelectropolymerization or chemical reductive polymerization which mayinvolve radical or radical anion generation include, without limitation,ethylene, propylene, butylene, higher alpha olefins, styrene, otheraromatic vinyl monomers, vinyl alcohol, vinyl acetate, fluorinated vinylmonomers, acrylates monomers, carbonate mononers, other ethylenicallyunsaturated monomers

Suitable diene monomers for cathodic electropolymerization include,without limitation, butadiene, substituted butadiene monomer, isoprenesubstituted isoprene monomers, or mixtures or combinations thereof.

Suitable crosslinking agents include, without limitation, compounds ofthe general formula (III)

A²-R″-A³  (III)

where A2 and A3 are the same or different and are selected from theheterocyclic compounds set forth above and where R″ is an alkenyl grouphaving between 1 and about 20 carbon atoms, where one or more of thecarbon atoms may be replaced by oxygen atoms, amino groups, amidegroups, ester groups, or mixtures thereof. Suitable crosslinking agentsfor cathodic electropolymerization include, without limitation, divinylalkyenyl crosslinking agents, divinyl aromatic crosslinking agents,other divinyl crosslinking agents or mixture or combinations thereof

Suitable substrates on which the coating of this invention may bedeposited include, without limitation, metal substrates, plasticssubstrates, ceramic substrates, or mixtures and combinations thereof.For substrates transparent substrate, the substrates include opticallytransparent ceramics such as glass, transparent plastics such aspolycarbonates, polyethylene, polypropylenes, polystyrenes, transparentmetals or mixtures and combinations thereof. Exemplary metals includingiron and iron alloys (e.g., steels, stainless steel, etc.), aluminum andaluminum alloys, copper and copper alloys, tungsten and tungsten alloys,nickel and nickel alloys, other transition metals and their alloys ormixtures or combinations thereof

Suitable conducting layer include, without limitation, any suitablemetal, metal alloy, metal oxide, polymer, and non-polymer surface, wherethe metal or metal alloys comprise gold (Au), platinum (Pt), indium tinoxide (ITO), iridium (Ir), rhodium (Rh), iron (Fe), titanium (Ti), Zinc(Zn), aluminum (Al) and other metal, metal oxide, or metal alloyelectrode and conducting electrodes, mixtures or combinations thereof.

Suitable particles for templates upon which the coating of thisinvention may be deposited include, without limitation, polymerparticles, polymer latex particles, metal oxide particles, ceramicparticles, salt particles, other conductive or non-conductive polymersor mixtures or combinations thereof. In certain embodiments, the polymerlatex particles are polyethylene latex particles, polypropylene latexparticles, polystyrene latex particles, natural rubber latex particles,liposomal particles, or mixtures or combinations thereof. In certainembodiments, the particles are capable of being removed by standardmethods such as washing, dissolving, etching, or other removal methodsgenerally known in the art.

Suitable surfactants for use in reversibly changing the properties ofthe coatings of this invention include, without limitation, fluorinatedsurfactants, anionic surfactants, non-ionic surfactants and/or cationicsurfactants or mixture or combinations thereof. Exemplary examples offluorinated surfactants include, without limitation,perfluorooctanesulfonic acid (PFOS), perfluorooctanoic acid (PFOA),perfluorononanoic acid (PFNA), DuPont Zonyl® FSO Fluorinated Surfactant,DuPont™ Forafac® fluorinated surfactants, or mixture thereof

Suitable anionic surfactants include, without limitation, anionicsulfate surfactant, alkyl ether sulfonates, alkylaryl sulfonates, ormixture or combinations. Preferred sodium or ammonium alcohol ethersulfate surfactants include those having the general formulaR¹O—(CH₂CH₂O)_(n)SO₃NH₄, where R¹ is a carbon-containing group includingan alkyl group, an aryl group, an alkaryl group, an aralkyl group ormixture thereof. Particularly preferred sodium or ammonium alcohol ethersulfate surfactants include short chain sodium or ammonium alcohol ethersulfate surfactants having between 2 and about 10 carbon atoms,especially, between about 4 and 10 carbon atoms and long chain sodium orammonium alcohol ether sulfate surfactants having between about 10 toabout 24 carbon atoms, more particularly, between about 12 and about 18carbon atoms, especially, between about 12 and about 14 carbon atoms.The sodium ammonium alcohol ether sulfate surfactants are prepared byreacting 1 to 10 moles of ethylene oxide per mole of alkanol, preferred,are prepared by reacting 3 moles of ethylene oxide per mole of alkanol.

Preferred alkylaryl sulfonates including, without limitation, alkylbenzene sulfonic acids and their salts, dialkylbenzene disulfonic acidsand their salts, dialkylbenzene sulfonic acids and their salts,alkyltoluene/alkyl xylene sulfonic acids and their salts,alkylnaphthalene sulfonic acids/condensed alkyl naphthalene sulfonicacids and their salts, alkylphenol sulfonic acids/condensed alkylphenolsulfonic acids and their salts, or mixture or combinations thereof.

Preferred alkyl ether sulfonates including, without limitation, alkylether sulfonates having the general formula R²[—(O—R³O)m-(R⁴O)n-(R⁵)]_(y) where: R²=alkyl, alkenyl, amine, alkylamine,dialkylamine, trialkylamine, aromatic, polyaromatic, cycloalkane,cycloalkene, R³, R⁴═C₂H₄ or C₃H₆ or C₄H₈ R⁴=linear or branched C₇H₁₄SO₃Xto C₃₀H₆₀SO₃X when y=1, R⁵=linear or branched C₇H₁₄SO₃X to C₃₀H₆₀ SO₃Xor H when y>1 but at least one R⁴ must be linear or branched C₇H₁₄SO₃Xto C₃₀H₆₀ SO₃X, M is greater or equal tol, n is greater or equal to 0,n+m=1 to 30+, y is greater or equal to 1, X=alkali metal or alkalineearth metal or ammonium or amine.

Suitable cationic surfactants include, without limitation, any cationicsurfactant such as monocarbyl ammonium salts, dicarbyl ammonium salts,tricarbyl ammonium salts, monocarbyl phosphonium salts, dicarbylphosphonium salts, tricarbyl phosphonium salts, carbylcarboxy salts,quaternary ammonium salts, imidazolines, ethoxylated amines, quaternaryphospholipids, gemini, bis or di quaternary ammonium surfactants such asbis quaternary ammonium halides of bis halogenated ethane, propane,butane or higher halogenated alkanes, e.g., dichloroethane ordibromoethane, or bis halogenated ethers such as dichloroethylether(DCEE). Preferred bis quaternary ammonium halides are prepared fromsubstituted dimethyl tertiary amines, where the substituent includesbetween about 4 and about 30 carbon atoms, preferably, between about 6and about 24 carbon atoms, and particularly, between about 8 and about24 carbon atoms, and where one or more of the carbon atoms can bereplace by an oxygen atom in the form of an ether and/or hydroxyl moietyand/or a nitrogen atom is the form of an amido moiety. Particularlypreferred bis quaternary ammonium halides hydrocarbons are prepared fromnaturally occurring acids, such as fatty acids synthetic acids, modifiednaturally occurring acids, or mixture or combinations thereof. Preferrednaturally occurring acids are those found in naturally occurring oilssuch as coconut oil, palm oil, palm kernel oil, soya, safflower oil,sunflower oil, peanut oil, canola oil, or from animal such as tallow oiland its derivatives. Preferred bis quaternary ammonium halides areprepared from disubstituted methyltertiaryamines, where the substituentsinclude between about 4 and about 30 carbon atoms, preferably, betweenabout 6 and about 24 carbon atoms, and particularly, between about 8 andabout 24 carbon atoms, and where one or more of the carbon atoms can bereplace by an oxygen atom in the form of an ether and/or hydroxyl moietyand/or a nitrogen atom is the form of an amido moiety, such asamidopropyltertiary amines, derived from the reaction of dimethylaminopropylamine(DMAPA) or similar terminated primary-tertiary diamines,reacted with the above mentioned oils or their corresponding fattyacids, or hydroxy acids. Other preferred cationic surfactants are dimeracids or anhydrides including alkylsubstituted maleic anhydride,alkylsubstituted diethylmalonic acid, or alkylsubstituted higher diacidssuch as azelaic acid (C9), trimer acids as NTA (nitriloacetic acid), andaconitic acid and trimetellic anhydride are useful though producting ahigher trimer. the tertiary amine may be accomplished by reaction of adiamine with a fatty acid or oil, reacting with one amine and thenconverting the other primary amine to tertiary by the addition oftetrahydrofuran, ethylene oxide, propylene oxide, butylene oxide,epichlorohydrin, or the like and further where the terminal hydrogens ofthe primary amine can be alkylated using formaldehyde/formic acidmixtures.

Suitable non-ionic surfactants include, without limitation, polyglycolscomprising polymers of ethylene oxide (EO), propylene oxide (PO), and/orbutylene oxide (BO), polyethyleneoxide polymers such as alcoholethoxylates and the alkylphenol ethoxylates, alkyl polyglycosides,sorbitan ester surfactants, distribution of the polyoxyethylene chain,polyoxyethylene alkylphenols, polyoxyethylene alcohols, polyoxyethyleneesters of fatty acids, polyoxyethylene mercaptans, polyoxyethylenealkylamines, nonionic surfactants containing an amide group, polyolester surfactants, and mixtures or combinations thereof

Suitable zwitterionic compounds include, without limitation: (1) anycompound having the general structure R⁶, R⁷, R⁸N⁺—R⁹—CO₂ ⁻, where R⁶,R⁷, and R⁸ are the same or different carbon-containing group, amidocarbon-containing group, ether carbon-containing group, or mixturesthereof, and R⁹ is an alkenyl group, alkenyloxide group or mixturesthereof; (2) any compound having the general structure R¹⁰(R⁷,R⁸N⁺—R⁹—CO₂ ⁻)_(n), where R⁷ and R⁸ are the same or differentcarbon-containing group, amido carbon-containing group, ethercarbon-containing group, or mixtures thereof, R⁹ is an alkenyl group,alkenyloxide group or mixtures thereof, and R¹⁰ is a multivalentsubstituent having a valency n between 2 and about 6, e.g., CH₂ moietywhen n is 2, a CH moiety when n is 3 and a C atom when n is 4; (3) anycompound having the general structureR¹²—C(O)—N(R¹¹)—R¹³—N⁺(R⁷,R⁸)—R⁹—CO₂ ⁻, where R⁷, R⁸, R¹¹ and R¹² arethe same or different carbon-containing group, amido carbon-containinggroup, ether carbon-containing group, or mixtures thereof, and R⁹ andR¹³ are the same or different alkenyl group, alkenyloxide group ormixtures thereof; (4) any compound having the general structureR¹⁴—[R¹⁵—C(O)—N(R¹¹)—R¹³—N⁺(R⁷, R⁸)—R⁹—CO₂ ⁻]_(m), where R⁷, R⁸ and R¹¹are the same or different carbon-containing group, amidocarbon-containing group, ether carbon-containing group, or mixturesthereof, R⁹, R¹³ and R¹⁵ are the same or different alkenyl group,alkenyloxide group or mixtures thereof and R¹⁴ is a multivalentsubstituent having a valency m between 2 and about 6; other similarammonium acid zwitterionic agent; or mixtures or combinations thereof.Preferred zwitterionic compounds are betaines such as cocamidopropylbetaine, 5-(1-piperidiniomethyl)-1H-tetrazolide, or similar zwitterioniccompounds. Other zwitterionic compounds for use in this inventioninclude, without limitation, phospholipids capable of assuming azwitterionic state such as phosphatidylcholine, phosphatidylserine,phosphalidylethanolamine, sphingomyelin and other ceramides, as well asvarious other zwitterionic phospholipids. Preferred sulfo-betaines andrelated zwitterionic compounds include, without limitation,N-Decyl-N,N-dimethyl-3-ammonio-1-propanesulfonate;Dimethylbenzyl-(3-sulfopropyl)ammonium;Dimethylethyl-(3-sulfopropyl)ammonium;Dimethyl-(2-hydroxyethyl)-(3-sulfopropyl)ammonium;4-n-Hexylbenzoylamido-propyl-dimethylammoniosulfobetaine;Methyl-N-(3-sulfopropyl)morpholinium;4-n-Octylbenzoylamido-propyl-dimethylammoniosulfobetaine;1-(3-Sulfopropyl)pyridium;N-Tetradecyl-N,N-Dimethyl-3-Ammonio-1-Propanesulfonate, or the like ormixtures or combination thereof.

Detailed Description of Section I Materials and Method Materials

Polystyrene (PS) latex microbeads (0.5 μm in diameter, 2.5 wt % solidsin aqueous suspension) are purchased from Polysciences, Inc. and areused without further purification. Acetonitrile (ACN), sodium n-dodecylsulfate (SDS), and tetrabutylammonium hexafluorophosphate (TBAH) areobtained from Sigma-Aldrich. The glass slides (BK 7) are acquired fromVWR. The gold surface is prepared by thermally evaporating gold (50 to100 nm thick) under high vacuum (10⁻⁶ bar) onto a BK 7 glass slide withchromium adhesion layer (˜10 nm thick). The Cr and Au deposition is doneat a rate ˜0.4 sec⁻¹ and ˜1.1 sec⁻¹, respectively, using a thermalevaporator (Edwards). The deionized water (resistivity ˜18 mΩ) used forthe dilution of PS particles is purified by a Milli-Q Academic® system(Millipore Cooperation) with a 0.22 micron Millistack filter at theoutlet. The monomers used in the electrochemical polymerization aresynthesized in our laboratory. The synthetic details of ethyl2-(2,5-di(thiophen-2-yl)thiophen-3-yl)acetate (Monomer 1, G0-3TCOORwhere R═CH₂CH₃), and 2-(2,5-di(thiophen-2-yl)thiophen-3-yl)acetic acid(Monomer 2, G0-3TCOOH) were performed according to the synthetic SchemeI.1:

The synthesis of G0-3TCOOR is carried out by first synthesizing ethyl2-(2,5-dibromothiophen-3-yl)acetate as reported in the literature.¹ Thesame literature procedure is modified to synthesize G0-3TCOOR. Ethyl2-(2,5-dibromothiophen-3-yl)acetate (6.4 g, 10 mmol) and2-(tributylstannyl) thiophene (15 g, 20 mmol) are added to a 30 mL dryDMF solution of dichlorobis(triphenylphosphine)palladium (1.3 g, 1.5mmol). After three freeze thaw cycles, the mixture is heated at 100° C.for 48 h. The mixture is cooled to room temperature and poured into abeaker containing 150 mL of water and subsequently extracted withCH₂Cl₂. The extracted CH₂Cl₂ mixture is dried with Na₂SO₄. Afterfiltering and evaporation of the solvent, the crude product is purifiedby chromatography on silica gel using toluene as an eluent. The finalproduct is obtained in 85% yield as pale yellow oil. Thecharacterization of the compound is found in accordance with theliterature.¹

Synthesis of 2-(2,5-di(thiophen-2-yl)thiophen-3-yl)acetic acid(G0-3TCOOH)

A total of 4 g of G0-3TCOOR is dissolved in methanol and added to a 20%aqueous sodium hydroxide solution (200 mL) The mixture is then refluxedfor 4 h. After removal of methanol, the aqueous solution is washed withether, acidified with concentrated HCl to pH 1 and extracted by ether.The ether solution is washed several times with water and evaporation ofether yielded 3.4 g G0-3TCOOH. The characterization of the compound isfound in accordance with the literature.²

Method of Preparing Superhydrophobic Films

The superhydrophobic-and-superlipophilic conducting surface isfabricated by simple two-step process such as (1) layering of PS latexmicrobeads onto conducting substrates like Au and ITO, and (2)electropolymerization of the monomer into the PS coated surface asillustrated in Scheme 2 as shown in FIG. 1. The layering of PS latexbeads is prepared using a similar procedure described earlier by Gradyand co-workers.³ As shown in Scheme I.2, the substrate is attached intothe dipper motor via a Teflon clip and is dipped into a solution of PSparticles (1 wt % in Milli-Q water) and SDS (34.7 mM) as spreadingagent. The substrate is then withdrawn vertically from the solution at alift-up rate of 0.1-0.3 mm/s. The substrate is then dried by suspendingit in air for a few minutes. After the layering of the latexmicrospheres, the monomer (5 mM in ACN with 0.1 M TBAH) iselectropolymerized onto the PS coated conducting surface (Au or ITO) asthe working electrode in a standard three electrode measuring cell withplatinum wire as the counter electrode and Ag/AgCl wire as the referenceelectrode. The electropolymerization is done using cyclic voltammetrictechnique in a fabricated electrochemical cell (Teflon made). Thepotential is scanned between 0 V to 1.1 V (and also 0V to 1.5 V) for 15cycles at a scan rate of 5 mV/s. The use of very low scan rate willresult to the formation of thicker polymer coatings. Note that it isalso possible to do this deposition of polymer by chronoamperometric orpotentiostatic methods. After electrodeposition, the film is washed inACN (3 times) to remove the excess monomer and physically adsorbedpolymer or oligomer, and a monomer free scan (in a solution of ACN with0.1 M TBAH as supporting electrolyte) is performed by using exactly thesame electrochemistry set-up and settings but for 1 CV cycle only.Finally, the electropolymerized film is thoroughly dried in vacuum forat least one hour prior to any characterizations.

Instrumentation Electrochemistry

Cyclic voltammetry is performed in a fabricated electrochemical cell(Teflon-made, with a diameter of 1.0 cm and volume of 0.785 cm³) using aconventional three-electrode cell using an Autolab PGSTAT 12potentiostat (Brinkmann Instruments). The potentiostat is controlled byGPES software (version 4.9).

Static Contact Angle

Contact angle measurements are done using a CAM 200 optical contactangle meter (KSV Instruments Ltd) with CAM 200 software. The experimentis carried out by slowly moving upward the sample stage with the sampleon top to come into contact with the liquid droplet (˜1 μL) that wassuspended at the tip of the micro syringe (200 μL). When using water forcontact angle measurements, the sample is only brought at a distance offew millimeters below the water droplet, and then the droplet iscarefully released to the surface. Unlike the other solvents, the waterdroplet will not adsorb or fall from the tip of the needle when incontact with the as-prepared superhydrophobic surface ofpoly(G0-3TCOOR)/PS (500 nm size) coated Au. The reading of the contactangle is done after 30 seconds when the droplet has been made into thesurface, and at least three trials are performed at various positions ofthe surface. The solvents used for contact angle measurements areMilli-Q water, hexadecane and diiodomethane.

Profilometry

The thickness of the films is acquired by surface profilometry using theAlpha-Step 200 profilometer. The Alpha-Step 200 accurately measuressurface profiles below 200 and up to 200 μm. A low stylus force of 5 mgis used during the scanning to avoid damaging the polymer surface. Themeasurements are done at least five times on different areas of the filmunder ambient and dry conditions.

Atomic Force Microscopy (AFM)

AFM analysis is carried out in a piezo scanner from AgilentTechnologies. The scanning rate is between 0.8-1.5 lines/s, and thescanning area is 5 μm×5 μm. Commercially available tapping mode tips(TAP300, Silicon AFM Probes, Ted Pella, Inc.) are used on cantileverswith a resonance frequency in the range of 290-410 kHz. The scanning ofthe PS coated Au and ITO is performed under ambient and dry conditions.All AFM topographic images (AAC tapping mode) are filtered and analyzedby using Gwyddion software (version 2.19). Note: Only the PS coatedsubstrates are scanned in the AFM. Because of the formation of a veryrough surfaces, the electropolymerized films on PS coated substrates arescanned in the SEM.

Four-Point-Probe

The conductivity measurements are determined with a four point probetechnique using the Keithley 2700 Multimeter Intergra Series. All filmsare measured at least five times on different area under ambient and dryconditions.

Attenuated Total Reflectance Fourier Transform Infrared (ATR-FTIR)

The ATR FTIR spectra are obtained on a Digilab FTS 7000 equipped with aHgCdTe detector from 4000 to 600 (cm-1) wavenumbers. All spectra aretaken with a nominal spectral resolution of 4 cm⁻¹ in absorbance mode.All films are measured under ambient and dry conditions.

Scanning Electron Microscopy

The morphology of the samples is examined by field emission scanningelectron microscopy (FE-SEM) using a JSM 6330F JEOL instrument operatingat 15 kV. Prior to SEM analysis, the films are thoroughly dried undervacuum for at least 24 hrs.

Analysis of Coatings

Referring now to FIG. 2, the cyclic potential deposition of thepoly(terthiophene) derivatives onto PS coated Au and bare Au usingmonomers 1 and 2 are shown. For the electropolymerization of G0-3TCOOR(FIGS. 2A and 2C), a constant increase of the oxidation peak (between0.95 V to 1.1 V) of the terthiophene monomer is observed from the 1stcycle to the 15^(th) cycle. After the first cycle, a new oxidation peakwith an onset 0.6 V appears. This anodic peak at a lower potential,which increases from the 2^(nd) cycle onwards, is attributed to theoxidation of the polymer. It has been reported before that the oxidationof the monomer is higher than the oxidation of the polymer, which is amore conjugated specie.⁴ Other anodic electropolymerizable monomers canbe used which incorporates thiophene, aniline, pyrrole, fluorene, andits fused heteroaromatic, oligomeric, and copolymeric derivatives. Whilethe present invention describes the use of conducting polymers viaanodic polymerization, it is possible to extend such design and sensingconcept to non-conducting polymers such as, but not limited to acrylate,styrene, vinyl functional groups via cathodic electropolymerization.Lastly, the electrochemical principles and methods described herein canalso be done using potentiostatic or chronoamperometric methods.

In the case of the electropolymerization of G0-3TCOOH onto PS coated Auand bare Au (FIGS. 1B and 1D), the oxidation peak of terthiophenemonomer increases and then decreases at higher CV cycles. Furthermore,rough CV curves are observed in both polymerizations, possibly due tothe formation of non-homogenous and coarse surfaces. The scanningelectron microscopy (SEM) analysis shows a rough surface has beenformed. The profilometry measurement validates that thicker films areformed with the electropolymerization of G0-3TCOOH than G0-3TCOOR.

The deposition of the conducting polymer onto the substrate is confirmedby doing a monomer free scan, sweeping the potential on same voltagewindow as the electropolymerization but for 1 CV cycle in the solventwith the supporting electrolyte only. The appearance of similar CVdiagrams (inset of FIGS. 2A-D) with the same reduction-oxidation (redox)couple as the electropolymerizations in the four CV curves (FIG. 2A-D)demonstrates the successful deposition of the conducting polymers ontoPS coated Au and bare Au in a stable and controlled manner. Theseresults are also confirmed with the various characterization techniquesdone below.

Referring now to FIG. 3, the static water contact angle measurements ofthe electropolymerized films are shown. The electropolymerization ofG0-3TCOOR on 500 nm size PS coated Au shows the highest contact anglewith a value of ˜154° (FIG. 3D), and thus considered superhydrophobicsurface. The electropolymerization of the less hydrophobic monomer(G0-3TCOOH) onto 500 nm size PS coated Au depicts a water contact angleof ˜145° (FIG. 3G). The electropolymerization of both monomers G0-3TCOORand G0-3TCOOH on bare Au gives water contact angle values of 103° (FIG.3B) and 32° (FIG. 3E), respectively. This result illustrates clearlythat the layers of the micron size particles play a very important rolein significantly increasing the water contact angle of the surface. Likethe micron-sized features on the surface of a lotus leaf, the 500 nmsize PS enhances the water resistivity of the artificial surface. Toexamine the effect of the size of the particles in relation to thesuperhydrophobic nature of the surface, the same conducting polymers(poly(G0-3TCOOR) and poly(G0-3TCOOH)) are deposited onto layers of PSmicrobeads with 100 nm size. These films reveal higher water contactangle than the films directly electropolymerized on bare Au (FIGS. 3Cand 3F). Their values are less than the films electropolymerized on PSwith 500 nm size. Thus, the contact angle of the electropolymerizedsurfaces increases with the size of the particles for both polymers(G0-3TCOOR and G0-3TCOOH), and the superhydrophobic surface is onlyattained with the layers of 500 nm size PS microbeads and with theelectropolymerization of the more hydrophobic monomer, G0-3TCOOR. As acontrol, the water contact angle of the 500 nm size PS is alsodetermined, and the value is 46° (FIG. 2A). The as-preparedsuperhydrophobic surface is also tested for static contact anglemeasurements using non-polar solvents with very low surface tension.Interestingly, the electropolymerized superhydrophobic film showscomplete absorption of the diiodomethane (FIG. 3H) and hexadecane (FIG.3I) with ˜0° contact angle, indicating superlipophilic behavior. Thisdemonstrates the extreme wetting properties of the films. With thisfinding, the fabricated film has potential applications for theeffective separation of organic solvents and possibly oils from waterduring an industrial discharge and oil-spills.

Table I.1 summarizes the dynamic water contact angle of thesuperhydrophobic⁵ polymer surface. The advancing and receding angles are˜154.0° and ˜151.0°, respectively.

TABLE I.1 Dynamic Contact Angle Measurements in Water (advancing andreceding angle) of Poly(G0-3TCOOR) on 500 nm size PS Coated Au DynamicWater Contact Angle Contact Angle (degrees) Advancing 154 Receding 151Hysteresis 3 (Advancing − Receding)The hysteresis⁶ of dynamic contact angle is determined to be thedifference between the advancing and receding angles, and is equivalentto 3°. With very low hysteresis (>5°), the superhydrophobic surface haspotential of rolling off the water droplet from its surface at very lowsliding angle.^(6,7) To test this premise, the superhydrophobic surfaceis tilted at an angle about 2.0°±0.5°, and water droplet is slowlyrelease from its surface. A movie clip is obtained, which confirms therolling of the water droplet from its surface at very low sliding angle.Therefore, the superhydrophobic surface can be used for self-cleaningpurposes like the lotus leaf.⁸

Table 1.2 summarizes the thickness and conductivity measurements of thepoly(G0-3TCOOR) on bare Au and 500 nm size PS coated Au at 0 V (dedopedstate) and 1.05 V (doped state).

TABLE I.2 Summary of Thickness and Conductivity Measurements of theElectropolymerized Films (Poly(G0-3TCOOR) and Poly(G0-3T COOH) on PSCoated (500 nm) and Bare Au Thick- Resis- ness* tivity** Conductivity #Electropolymerized Film (μm) (ohm/square) (Siemens cm⁻¹) 1 5 mMG0-3TCOOR on bare Au  4-12 184.21 4.52-13.57 CV: 5 mV/sm 15 cycles, 0 Vto 1.1 V 2 5 mM G0-3TCOOR on PS Coated Au 2.5-6.5 362.56  4.24-11.03\CV: 5 mV/sm 15 cycles, 0 V to 1.1 V 3 5 mM G0-3TCOOR on PS Coated Au2.5-6.5 166.17 9.25-24.07 CV: 5 mV/sm 15 cycles, 0 V to 1.1 V Apply+1.05 V, 30 mins. 4 5 mM G0-3TCOOR on PS Coated Au 2.5-6.5 308.184.99-12.98 CV: 5 mV/sm 15 cycles, 0 V to 1.1 V Apply +0.85 V, 30 mins. 55 mM G0-3TCOOH on bare Au 30-50 67.89 2.94-4.90  CV: 5 mV/sm 15 cycles,0 V to 1.1 V 6 5 mM G0-3TCOOR on PS Coated Au 20.5-40.5 270.410.91-1.80  CV: 5 mV/sm 15 cycles, 0 V to 1.1 V *Profilometry, **FourPoint Probe (measurements were done at least five times in differentarea)The thickness measurements of the poly(G0-3TCOOR) on PS coated Au andbare Au are estimated to be between 2.5-6.5 μm and 4.0-12.0 μm,respectively. Thicker films are made with the electrodeposition ofpoly(G0-3TCOOH) on PS coated Au and bare Au (˜30-50 μm and ˜20.5-40.5μm, respectively) than the poly(G0-3TCOOR). The conductivitymeasurements of poly(G0-3TCOOR) on PS coated Au at neutral state (0V) isdetermined to be between ˜4.24-11.03 Scm⁻¹. The conductivity of the filmincreases upon doping at 1.05 V, and its value is estimated to be9.25-24.07 Scm⁻¹. At 0.85 V, the conductivity of the film slightlyincreased (4.99-12.98 S cm⁻¹) as compared to the dedoped state(˜4.24-11.03 Scm⁻¹). By applying a constant positive potential (doping),the conductivity of the conjugated polymers is known to change. Forinstance, its conductivity is largest for the doped state and decreasesfor the dedoped state.⁹ The conductivity values of poly(G0-3TCOOH) areless than the conductivity of poly(G0-3TCOOR). This highlights the roleof conductivity and doping towards the wetting behavior. This resultsshow the variable electrical conductivity of the film.

Referring now to FIG. 4, the surface morphology studies of the differentsurfaces using AFM and SEM microscopies are shown. The AFM reveals(FIGS. 4A and 4B) highly ordered and closely-packed monolayer arrays oflatex microspheres on Au substrate. Upon electrodeposition of theconducting poly(terthiophene) on PS coated Au, the morphology of thesurface changes as seen in the SEM images (FIGS. 4C and 4D). Ahierarchical two scale features are observed in the surface of thesuperhydrophobic polymer film (poly(G0-3TCOOR)/PS (500 nm size) coatedAu). This finding explains the superhydrophobicity of the surface thatresembles the lotus leaf with micron and nanometer scale roughness. Arougher surface (FIGS. 4E and 4F) is noticed with theelectropolymerization of the same monomer on bare Au. These measurementsconfirm the role of morphology in observing the unique wetting behavior.

Referring now to FIG. 5, the ATR IR analysis of the electropolymerizedfilms are described: (1) poly(G0-3TCOOR) on PS coated Au and bare Au and(2) poly(G0-3TCOOH) on PS coated Au and bare Au. CH stretchingvibrations (between 2800-3000 cm⁻¹) are shown in all electropolymerizedfilms. Moreover, higher CH stretching vibration appears (above 3000cm⁻¹) in the electropolymerized poly(terthiophene) films, which isreported as the CH stretch in the thiophene ring.¹⁰ A strong C═O peak isobserved with the electrodeposition of poly(G0-3TCOOR) on PS coated andbare Au. This peak is also seen in the poly(G0-3TCOOH). With thepoly(G0-3TCOOH) film, a broad OH stretching vibration is discerned,which does not appear with the poly(G0-3TCOOR) film. The spectrum of the500 nm sized layers of PS is also taken to compare with theelectropolymerized poly(terthiophene) films. It also shows CH and C═Cstretching vibrations and a doublet peak at 1500 cm⁻¹ that is assignedto CH bending vibration.¹¹ XPS measurements are also performed toconfirm the presence of the poly(terthiophene) on the surface (discussedbelow). These measurements confirm the composition and the incorporationof polystyrene and conducting polymer in the same film.

Table I.3 summarizes the static contact angle of the artificialsuperhydrophobic conducting polymer surface at different pH values ofwater. From pH˜1.0 to pH˜13.0, the poly(G0-3TCOOR)/PS (500 nm size)coated Au demonstrates superhydrophobicity with contact angle greaterthan 150°.

TABLE I.3 Static Contact Angle Measurements of the ElectropolymerizedG0-3TCOOR onto PS (500 nm size) Coated Au Using Water with Different pHθ_(Left) θ_(Right) pH (degree) (degree) 0.99 150.04 ± 0.66 150.15 ± 0.102.08 152.89 ± 1.07 151.44 ± 0.90 2.92 150.57 ± 0.28 152.59 ± 1.88 4.05152.46 ± 2.72 152.94 ± 3.01 5.02 151.33 ± 2.31 150.86 ± 2.97 6.14 151.66± 1.85 152.50 ± 0.66 7.08 153.04 ± 1.90 153.06 ± 2.83 8.78 154.28 ± 0.34153.55 ± 0.59 9.98 151.11 ± 0.82 151.00 ± 0.18 11.02 153.49 ± 0.37151.64 ± 1.18 12.00 151.27 ± 2.40 151.52 ± 2.04 13.07 151.15 ± 2.93150.89 ± 2.24

These results show the pH dependence of the wetting behavior of thefilms. This result shows that the as-prepared surface can be possiblyused for water resistivity even at corrosive environments and wide pHrange.

Referring now to FIG. 6, the static contact angle of thesuperhydrophobic surface at different temperatures of water aresummarized. At low temperatures (starting at ˜4° s), itssuperhydrophobicity is maintained. Similarly, at high temperatures (˜80°and below), a water contact angle above 150° is also sustained. Thisresult proves the thermal stability of the superhydrophobic surface at awide range of temperatures.

Referring now to FIG. 7, the long term stability of the superhydrophobicsurface, poly(G0-3TCOOR)/PS (500 nm size) coated Au are demonstrated.This study is accomplished by measuring the static water contact angleof the surface over time. The film is kept under dry and ambientconditions when not analyzed by contact angle. After keeping the film inthe said condition for about 5 months, the surface still upholds itssuperhydrophobicity with water contact angle value of ˜150°.

Referring now to FIG. 8, the stability of the superhydrophobic propertyof the electrodeposited poly(G0-3TCOOR) onto 500 nm size PS coatedsubstrates as compared to other electropolymerized films (usingcommercially available monomers) fabricated using the same scheme(Scheme 1) are illustrated. This study is carried out by allowing thewater droplet to sit on the electropolymerized films and simultaneouslymeasuring the static contact angle over time. For the poly(G0-3TCOOR) onPS (500 nm size) coated Au, its superhydrophobicity is maintained for atleast 20 minutes. The electropolymerization of poly(G0-3TCOOR) is alsoperformed onto 500 nm size PS coated ITO to confirm the earlier resultwith the PS coated Au. Likewise, a water contact angle greater than 150°is preserved with the electropolymerized film on PS coated ITO for atleast 20 minutes. In the case of poly(G0-3TCOOH) on 500 nm size PScoated Au (starting water contact angle of ˜145°), its contact angleslowly decreases over time and the value drops to ˜125° after 20minutes. It is possible that the COOH functional groups of the polymerfilm slowly forms H-bonding with the water droplet, and hence allowingthe slow penetration of the water into the polymer film. With the otherelectropolymerized films (also deposited on 500 nm size PS coated Au)using the commercially available monomers, their contact angledramatically decreases over time and are eventually consideredhydrophilic surfaces (water contact angle <100°). This result highlightsthe advantage of using the synthesized and designed monomers of theaforementioned thiophene derivatives for the fabrication of stablesuperhydrophobic surfaces with long term water resistivity. Other anodicelectropolymerizable monomers can be used which incorporates thiophene,aniline, pyrrole, fluorene, and its fused heteroaromatic, oligomeric,and copolymeric derivatives.

Referring now to FIG. 9, the reversible wettability, fromsuperhydrophobic to hydrophilic, and the relation to the reversibleelectrochromic properties of the poly(G0-3TCOOR)/PS coated Au. After aconstant oxidation potential of 1.05 V (doping) is applied to the film,its water contact angle decreases to 60° are depicted. With the samesurface and applying 0 V to dedope the polymer film, its constant anglereturns back to >150°. For two consecutive cycles, the water contactangle of the poly(G0-3TCOOR)/PS (500 nm size) coated Au is able toreverse back and forth from superhydrophobic)(>150° to hydrophilic)(<65°status depending upon the potential applied to the polymer film.Accompanying the change in the wettability of the surface is also thechange in the electrochromic property upon doping (apply 1.05V) anddedoping (apply 0V). Photo images of the same polymer film at dry stateare taken immediately after applying a doping and dedoping potentials.From the images, the polymer film exhibits a distinct orange color atneutral (dedoped) state and dark green to black color at charged (doped)state. To verify the reversible wettability and electrochromicproperties of the polymer film, the poly(G0-3TCOOR) is deposited on bareAu. Likewise, the electropolymerized film on Au is subjected to dopingand dedoping by applying 1.05 V and 0 V, respectively. The film alsoshowed reversible wettability from hydrophobic)(˜100° to hydrophilicstates)(˜60° for the same number of cycles. The reversibleelectrochromic property of the film is also displayed by the change incolor of the film from orange (at 0 V) to dark green (at 1.05V). Thisresult indicates that the reversibility of the wettability andelectrochromic properties of the surface is only due to thepoly(terthiophene) and there is no contribution from the underlying PSlayers. The wettability and electrochromism of the surface can be easilytuned and controlled by simply adjusting the potential of the film. Thisalso implies that other electro-optical properties(transmission/absorption, fluorescence, charge transfer, non-linearoptical properties, etc.) of the conducting polymer film can be tunedtogether with the wetting/surface energy properties of the film.

To study further the electrochromic property of the polymer film, theelectrodeposition of poly(G0-3TCOOR) is done on bare ITO so that UV-Vismeasurements can be performed as shown in FIG. 10. The change in colorof the film from orange to dark green is again observed upondedoping/doping. The contact angle is able to reverse from 110° (dedopedstate) to 50° (doped state). From the UV-Vis spectrum, a broad peak(λ_(max)˜440 nm) is shown with the film at neutral state (0 V), which isdue to the absorption of the poly(terthiophene) ring.¹² This peakdecreases and another broad peak appears at 740 nm at doped state (1.05V). The broad peak at 740 nm is attributed to the formation of theradical cation called polaron.¹³

Referring now to FIG. 11, the current response versus time(chronoamperommetric measurements) upon applying 1.05 V and 0 V to thepoly(G0-3TCOOR) onto 500 nm size PS coated Au are shown. The sameprofile is observed with application of 1.05 V and 0 V to thepoly(G0-3TCOOR) on bare Au and bare ITO.

Referring now to FIG. 12, the XPS survey scan of the superhydrophobicfilm poly(G0-3TCOOR)/PS coated Au before and after doping are presented.The conversion of the superhydrophobic surface into hydrophilic afterapplying a constant oxidation potential is possibly due to the charging′of the polymer film. Consequently, the negatively charged counter ion(PF⁶⁻ from the TBAH supporting electrolyte) in solution will be insertedinto the positively charged polymer film to maintain its neutrality. Theappearance of F1s and P 2p peaks in the survey scan after doping (apply1.05 V) the polymer film validated the insertion of the PF⁶⁻ counter ionas a result of the charging of the polymer film. These peaks are notshown at dedoped state (0 V).

The high resolution XPS scans as shown in FIG. 13 confirm the results ofthe survey scan. After applying 1.05 V to the poly(G0-3TCOOR)/PS Au, anobvious F 1s and P 2p peaks appear on the high resolution XPS spectrum.Furthermore, the S 2p, C 1s, and O 1s peaks remain constant, signifyingthe stability of the poly(terthiophene) even with the application of adoping potential. The presence of S 2p peak suggests the formation ofthe poly(terthiophene) films onto the PS coated Au. And theelectropolymerized film is thick since the Au 4f peak is no longer seenby the XPS scan, which corroborates the profilometry measurement. Thisdata authenticates the results of the other characterization techniquesbased on the doping and dedoping mechanisms of the conducting polymer.

Referring now to FIG. 14, the contact angle measurements ofpoly(G0-3TCOOR)/PS (500 nm) Au and other substrates as control areillustrated. After the spin coating of a fluorinated surfactant (S760P), the once superhydrophobic-and-superliphophilic surface is nowconverted into superhydrophilic and liphophobic. This novel behaviorshowing the transformation from superhydrophobic (WCA>150°) tosuperhydrophilic (WCA˜0°) and from superliphophilic (˜0 degree C.A inhexadecane and diiodomethane) into liphophobic (>80° CA in hexadecaneand diiodomethane) is only exhibited by poly(G0-3TCOOR)/PS (500 nm) Au.The same experiment is also done with the other substrates to comparethe earlier film (poly(G0-3TCOOR)/PS (500 nm) Au. This highlights thepossibility of using surfactants to modify the wetting behavior of theexisting system based primarily on changes in the surface energy ormorphology with the use of other surfactants.

Other Embodiments

Other anodic electropolymerizable monomers can be used whichincorporates thiophene, aniline, pyrrole, fluorene, and its fusedheteroaromatic, oligomeric, and copolymeric derivatives. While this workemphasizes the use of conducting polymers by anodic polymerization, itis possible to extend this method and design to non-conducting polymerssuch as acrylate, styrene, vinyl functional groups via cathodic. Itshould also be noted that electrochemistry can be done in variousshapes, sizes, and geometries of the electrode including a choicebetween potentiodynamic and potentiostatic or chronoamperometricmethods. It is possible that this work can be extended to large areasurfaces or confined dimensional surfaces and interfaces where the abovementioned embodiments are possible Important applications of suchcoatings can be in the form of anti-wetting, filtration, anti-corrosion,de-icing, anti-microbial, electrochromic, and electrophoretic orelectro-wetting applications where the wetting properties of the filmplay an important role.

REFERENCES CITED IN SECTION I

The following references were cite in the section of the specification:

-   1 Taranekar, P.; Fulghum, T.; Baba, A.; Patton, D. and Advincula, R.    Langmuir 2007, 23, 908-917.-   2 Yassar, A.; Moustrou, C.; Youssoufi, H. K.; Samat, A.;    Guglielmetti, R.; F. Garnier, F. Macromolecules 1995, 28, 4548-4553.-   3 Marquez, M.; Grady, B. P. Langmuir 2004, 20, 10998-11004.-   4 Roncali, J., Chem. Rev. 1992, 92, 711-738-   5 Qu, M.; Zhao, G.; Cao, X.; Zhang, J. Langmuir 2008, 24, 4185-4189.-   6 Darmanin, T.; Guittard, F. J. Am. Chem. Soc. 2009, 131, 7928-7933.-   7 Synytska, A.; Ionov, L.; Grundke, K.; Stamm, M. Langmuir 2009, 25,    3132-3136.-   8 Blossey, R. Nat. Mater. 2003, 2, 301-306.-   9 Georgiadis, R.; Peterlinz, K. A.; Rahn, J. R.; Peterson, A. W.;    Grassi, J. H. Langmuir. 2000, 16, 17, 6759-6762.-   10 Fabre, B.; Lopinski, G. P.; Wayne, D. M. J. Phys. Chem. B. 2003,    107, 14326-14335.-   11 Lu, X.; Zhou, J.; Zhao, Y.; Qiu, Y.; Li, J. Chem. Mater. 2008,    20, 3420-3424.-   12 Xia, C.; Park, M-K.; Advincula, R. Langmuir 2001, 17, 7893-7898.-   13 Ikeda, T.; Higuchi, M.; Kurth, D. G. J. Am. Chem. Soc. 2009, 131,    9158-9159.-   14 (a) Schopf, G.; Koβmehl, G. Advances in Polymer Science:    Polythiophenes-Electrically Conductive Polymers. Spinger.    1997, 80. (b) Koβmehl, G.; Kabbeck-Kupijai, D.; Niemitz, M. Chiuz.    1990, 24, 106. (c) Niemitz, M.; Koβmehl, G. Angew. Makron. Chem.    1991, 185-186, 147. (d) Koβmehl, G.; Niemitz, M. Synth. Met. 1991,    41, 1065.

Detailed Description of Section II Superhydrophobic-SuperoleophilicPolythiophene Films with Tunable Wetting and Electrochromism Summary ofInvention of Section II

A non-fluorinated polythiophene film with dual superhydrophobic andsuperoleophilic wetting properties involving 2-D assembly of polystyrene(PS) latex particles and electropolymerization was demonstrated. Thephenomenon is stable at wide temperatures and pH ranges. It is easilyand rapidly reversed with voltage or surfactant coincident withelectrochromism.

Introduction of Section II

There is much interest in superhydrophobic surfaces as inspired by thenon-wetting properties of the lotus leaf.¹ It can give a water contactangle greater than 150° with only 2-3% of the water droplet coming intocontact with its surface—a common test for designating syntheticsuperhydrophobic surfaces.¹ The high water repellency is well worthmimicking because of the myriad industrial and practical applicationsnamely self-cleaning coatings, anti-fouling marine coatings,microfluidics, anti-biofouling, and anti-ice adhesion properties.² Herewe report a novel and facile preparation of a non-fluorinatedsuperhydrophobic-superoleophilic polythiophene coating withreversibility to a superhydrophilic-and-oleophobic surface viaelectrochemical polymerization on a two-dimensionally (2-D) layeredcolloidal particle template. Interestingly, such films exhibit bothsimultaneous reversible electrochromic and extreme wettabilityproperties by simply changing the voltage (potential) ex-situ. Suchreversible wettability property can result in highly controlled wettingbehavior with possible dual applications in self-cleaning coatings,channeling of flow properties, controlled membrane separations, andregenerable surfaces together with electro-optical functionality(electrochromic)—by a mere switch of the applied potential.

Artificial superhydrophobic surfaces can be accomplished by developing adual-scale roughness structure and tuning of surface energy.³ Mostreports^(2,3) on synthetic superhydrophobic surfaces have beenfabricated using fluorinated polymers and small molecule compounds,which are markedly known as low surface energy coating materials.⁴Fluorinated small molecule compounds in particular are more expensiveand deemed to have some detrimental effects with bio-accumulation to theenvironment.^(5,6) Therefore, these concerns necessitate the developmentof non-fluorinated superhydrophobic coatings with other inherentlyuseful functionality or properties.^(7,8)

To date, electrodeposited electrically conducting polymers mostly withfluorinated functional group have been demonstrated to confer water andalso oil resistance.⁹ There are only few accounts on non-fluorinatedconducting polymers usually with longer alkyl side chain that show highwater repellency.¹⁰ However, earlier reports about the use ofnon-fluorinated conducting polymers for anti-wetting surface coatingshave not illustrated superhydrophobicity and superoleophilicity(co-existence of two surface properties) with reversible wettability andelectro-optical properties via ex-situ potential switching. Conductingpolymers in general and polythiophenes in particular, have uniqueelectro-optical and mechanical properties making them useful for displaymaterials, semi-conductors, electrochromic devices, fluorescentmaterials, non-linear optical materials, and various types of industrialcoatings for anti-corrosion and anti-static purposes etc.¹¹

Unlike other methods of creating synthetic superhydrophobic coatingssuch as laser/plasma/chemical etching, electrospinning, andlayer-by-layer assembly,¹² electrochemical deposition of conductingpolymers has remained relatively unexplored for such applications. Theelectropolymerization technique offers several advantages in that it canbe site-directed and deposited over large surface areas. It has beenapplied on a variety of electrode surfaces mostly based on metal orsemi-conductor or transparent substrates like Au, Ag, Al, stainlesssteel, indium tin oxide (ITO), etc.,¹³ and it can be done by cyclicvoltammetry or potentiostatic methods. Moreover, electropolymerizationcan enable the control of thickness, surface growth, and morphologyusing various parameters (e.g., scan rate, potential window, etc.).¹³For patterning and creating surface features, the vertical depositionmethod of 2-D nanoparticle colloidal layering using a Langmuir-Blodgett(LB) like-technique′ has not been broadly used for site directed ortemplated electrodeposition. Yet, this technique has proven to beeffective in making highly-ordered and closely packed array features oflatex nanospheres on flat surfaces that can influence film morphologythrough periodic surface structures.

Referring to FIGS. 15A-H, a two-step process towards the formation ofsuperhydrophobic-and-superoleophilic conducting polymer nanostructuredsurface is shown. AFM topography 2D images (3D on inset) of LB-likesurface layering of PS nanoparticles: (B) 200 nm size, (C) 350 nm, and(d) 500 nm. IR imaging showing (E) 2D and (F) 3D images with IR spectrafocused on (G)C—H stretch (area in dark gray or green) and (H) C═Ostretch (area in light gray or cyan) regions. Note: Scanning area is176×176 μm².

To create a surface energy controlled and morphologically nanostructuredpolythiophene film, a two-step approach was applied starting with thelatex assembly of polystyrene (PS) nanoparticles onto a flat conductingsubstrate. This created a 2D surface with high regularity of PSordering. A highly-ordered and closely-packed monolayer assembly of thecolloidal crystals in hexagonal packing arrangement is shown in FIG.15B-D of various nanoparticle sizes. The monolayer ordering of thespherical nanoparticles had been previously reported to be dependent onthe vertical withdrawing speed of the LB-like technique and theconcentration of the nanoparticles and surfactant (sodium n-dodecylsulfate or SDS) in solution.¹⁴ To complete the formation of thenanostructured film, this was then followed by a cyclic voltammetric(CV) electrodeposition as shown in FIG. 16 of the polythiophene film(structure in FIG. 15A). After washing with a solvent similar to thatused for CV, the film was characterized and immediately investigated forits wetting behavior. For compositions, the attenuated total reflectanceinfrared (ATR IR) spectra are shown FIG. 17 confirms theelectrodeposition of the polythiophene or poly(G0-3TCOOR) atop the layerof PS nanoparticle as shown by the characteristic peaks ofpoly(thiophene): C═O stretch (1729 cm⁻¹), linear CH stretch (2847-3028cm⁻¹), aromatic CH stretch (3035-3161 cm⁻¹), C═C stretch (˜1660 cm⁻¹)and O—C stretch (˜1275-1391 cm⁻¹). Moreover, the FT-IR imaging in micronscale (FIGS. 15E and 15F) reveals a high amount of C—H functional groups(FIG. 15G) on the surface (dominance in the dark gray or green colorregion, FIG. 15E), which occurs in the region of 2829-3159 cm⁻¹ (averageof several measurements on different regions). Also, the C═O signaturepeak (FIG. 15H) of poly(G0-3TCOOR) is more pronounced in the light gray(blue color) region and minimally present in some areas of the dark gray(green colored) region. Thus, from the IR chemical map (FIG. 15E), ahigh or complete coverage of poly(G0-3TCOOR) is achieved on the surface.Also, the as-prepared polymeric surface is rough, as clearly seen in theIR 3D image (FIG. 15F).

Referring to FIGS. 18 A-G, contact angle measurements of poly(G0-3TCOOR)onto 500 nm PS/Au in (A) water, (B) diiodomethane, and (C) hexadecaneare shown; while (D) shows low 24×36 mm and (E) high magnification SEMimages of poly(G0-3TCOOR) onto 500 nm PS/Au at 4×3 mm. Also adistinction between the: (F) Doped (1.05 V, 30 mins), and (G) dedoped (0V, 30 mins) morphologies at wide area of 800×900 μm. Sub-micron scaleroughness can be observed in FIG. 19.

As shown in FIG. 18A, a superhydrophobic film is created as evidenced bythe high advancing (θ_(adv)) and receeding (θ_(rec)) contact anglevalues of 154°±1 and 151°±1, respectively. Similarly, the film attains awater contact angle of 154°±1 in static measurements. With a very lowhysteresis (θ_(adv) minus θ_(rec)) of only ˜3°, the film is expected toexhibit a self-cleaning effect. To validate this claim, the film wastested by dropping the water (˜1-2 μL) onto its surface when thesubstrate was inclined at a very low angle (as shown in FIG. 20). Thewater droplet freely rolls off the surface at the sliding angle of 2°±1.These evidences suggest that the superhydrophobic nanostructured filmbehaves along the Cassie-Baxter model^(15,16) (Equation II.1), whichdescribes the liquid droplet to be sitting and not pinned atop thenanocomposite surface of the solid protuberances and air:

cos θ*=−1+φ_(s)(1+cos θ)  (II.1)

where θ* is defined as the apparent contact angle, θ as equilibriumcontact angle, and φ_(s) as the fraction of solid-liquid contact. Thismodel assumes that a certain percentage of the liquid-solid interface isreplaced with a liquid-gas interface.¹⁵ The artificial superhydrophobicsurface reveals a hierarchical roughness that comprises of a regularglobular structures (>500 nm size) smeared with smaller nanometer scaleasperities (FIG. 18D and FIGS. 19A-H). Foam-like structures are alsoseen in the morphology, which are typical for polymer coatingsfabricated under these controlled conditions.¹⁶ Moreover, the SEM imagesdivulge that the polythiophene converges or aggregates around the PSparticles creating nanometer roughness (FIG. 18E). The importance of theunderlying layer PS particles to enable superhydrophobicity isdemonstrated by measuring the contact angle of an electropolymerizedfilm (poly(G0-3TCOOR)) on planar Au substrate without the colloidalnanoparticles. This film depicts a water contact angle of only 103°±1(FIG. 21). On the other hand, the contact angle augments to 111°±1 whenthe same polymer film was electrodeposited even onto the layers ofdisordered 100 nm PS particles on Au substrate. Thus, the contact angleincreases with increasing roughness as augmented by the PS particleseven at this size and organization. This trend is also observed with theelectropolymerization of a more hydrophilic polythiophene(poly(G03TCOOH) e.g., contact angle has increased to 140°±4 from 32°±1.These results further validate the behavior of the film following theCassie-Baxter model since both hydrophilic (poly(G03TCOOH) on Au) andhydrophobic (poly(G0-3TCOOR) on Au) films has shown a considerableincrease in contact angle. The increase in contact angle has beenexplained to be a contribution of surface roughness and air cavitiesthat are trapped between the droplet and solid surface minimizing thecontact area.¹⁷ This is unlike the Wenzel's model (Equation11.2),^(16,18) which suggests that the contact angle of the surface willincrease or decrease upon surface texturing when the original surface(without roughness) is hydrophobic (water contact angle (WCA)>90°) orhydrophilic (WCA<90°), respectively:¹⁷

cos θ*=r cos θ  (II.2)

where r is defined as the ratio of the actual over apparent surface areaof the substrate. Note that the superhydrophobicity is not attained withthe layers of 500 nm PS particles alone (WCA˜46°±1) and even with thehydrophilic electropolymerized film (poly(G03TCOOH) onto the layers of500 nm PS particles (140°±4). These results confirm that thesuperhydrophobicity is due to the synergistic effect of the twoimportant factors namely: (1) hierarchical roughness, which are thenanometer scale asperities within the sub-micron scale geometricalstructures and (2) low surface energy on the surface, both attributesthat have been found in a lotus leaf.^(1,3)

Interestingly, the film maintains its superhydrophobicity even with high(˜80° C.) and low (˜4° C.) temperatures of water (FIG. 22), which is noteasily attained by many artificial superhydrophobic polymer surfaces.With this behavior, the film may find potential applicationsparticularly in thermal and anti-ice adhesion coatings (to be exploredin future). The film also shows a strong repellency to water (WCA>150°)at very low (pH˜1.0) and very high (pH˜13.0) pH values, such as in acorrosive environments (Table II.1).

TABLE II.1 Static Water Contact Angle Measurements of theSuperhydrophobic Film (poly(G0-3TCOOR) onto 500 nm PS layer on Au) atDifferent pH Values of Water θ_(Left) θ_(Right) pH (degree) (degree)1.00 151 ± 1 151 ± 1 2.08 153 ± 1 151 ± 1 2.92 151 ± 1 153 ± 2 4.05 153± 3 153 ± 3 5.02 151 ± 2 151 ± 1 6.14 152 ± 2 153 ± 1 7.08 153 ± 1 153 ±3 8.78 154 ± 1 154 ± 1 9.98 151 ± 1 151 ± 1 11.02 154 ± 1 152 ± 1 12.00151 ± 2 152 ± 2 13.07 151 ± 2 151 ± 1

Thus, the film has attractive properties for potential applications tomany industrial and marine coatings. Moreover, the superhydrophobicityof the nanostructured film can be sustained for a longer period of timeabout >146 days. This is done by measuring repeatedly over time thewater contact angle of the same film, which was kept under dry andambient conditions. The fabrication scheme was also reiterated byelectropolymerization of commercially available thiophene monomerderivatives to form poly(bithiophene), poly(terthiophene), andpoly(3,4-ethylenedioxythiophene) onto the layers of 500 nm PS particles.The electropolymerization of the synthesized monomer ofterthiophene-ester derivatives or G0-3TCOOR (see Scheme II.1) showssuperior quality that exhibits longer superhydrophobicity compared tothe commercially available monomers (FIG. 23). The pre-grafted estermoieties of the terthiophene electropolymerizable pendant group may havecontributed to the formation of a rougher and porous surface. Moreover,no fluorination or silane treatment was employed unlike most reportedschemes for superhydrophobic surfaces including the use of conductingpolymers.^(9,17,19)

The same film was also examined for static contact angle measurements indiiodomethane (γ_(L)=50.0 mN/m) and hexadecane (γ_(L)=27.6 mN/m). Theseare commonly used solvents to test for surface oleophobicity (oilresistance) with surface tension (γ_(L)) much lower than water(γ_(L)=72.8 mN/m).⁹ Interestingly, this superhydrophobic films alsoexhibited superoleophilic character (thus coexistence ofsuperhydrophobic and superoleophilic) as shown by the nil contact anglevalues in both organic solvents (FIGS. 16B and 16C)—a rare and uniqueproperty exhibited by the same surface. This means that the film may beuseful for the selective separation of organic solvents or oils in anorganic solvent or oil and water mixtures. The real time video clip ofthe contact angle measurements clearly demonstrates the strong defianceof the film to water and complete intake of the hexadecane anddiiomethane (FIG. 24).

Referring now to FIGS. 25 A-C, reversible wettability andelectro-optical properties are shown. FIG. 25A shows static watercontact angle analysis of poly(G0-3TCOOR) on PS-templated Au (solidline) and poly(G0-3TCOOR) on bare Au (broken line) via potentialswitching between 1.05V (doping) and 0V (dedoping) are shown. FIG. 25Bshows UV-V is measurements of the doped (light gray orange colored film)and dedoped (dark gray or dark green colored film) poly(G0-3TCOOR)electrodeposited on ITO are shown. FIG. 25C shows XPS survey scans ofthe doped (broken line curve) and dedoped (solid line curve) film areshown. Note the doping and dedoping of the films were carried out in ACNwith the supporting electrolyte (0.1 M TBAH) using the sameelectrochemistry set-up (FIG. 15A) having three electrode system withthe electrodeposited film on Au as the working electrode.

One of the many advantages of using a conducting polymer for coatings isthe possibility to control the wettability and electro-optic alproperties of the surface at the same time. In principle, this can bedone simply by adjusting the electrical potential, which may be a fasterway (e.g., few seconds) to switch surface wettability unlike othermethods, which require high temperature, UV irradiation, change inchemical composition of surface, or surfactant treatment.²⁰ This dualproperty is of significant interest in switchable wettable surfaces forapplications in dual smart or stimuli-responsive devices such asintelligent microfluidic switches, semiconductor transparent coatings,sensors, electrochromic devices, and so on.^(17,20) Previously, Lahannet al.²¹ demonstrated reversibly wettable switching surfaces bycontrolling the electrical potential of a low densecarboxylate-terminated self-assembled monolayer (SAM)s on Au surface.However, the change in surface wettability is small (˜20°), which limitsits practical applications and possibly regenerability. Also, Manukyanet al.²² recently reported the local reversible switching of wettingstates (from Cassie-Baxter state to Wenzel state and reverse) in asuperhydrophobic surface using an electrical potential. Nevertheless, adramatic change in the surface wettability of their film was notillustrated.

FIG. 25A shows the significant change in the wettability of thepoly(G0-3TCOOR) film upon changing the electrical potential ex-situ,which is reversible for several cycles. Upon application of 1.05 V(doping) using the same electrochemistry set-up with the three electrodesystem on FIG. 15A, the superhydrophobic film becomes hydrophilic)(˜60°with a dramatic decrease in water contact angle by more than 90°.Similarly, the contact angle of the poly(G0-3TCOOR) on Au (control film)has changed from ˜100° to ˜60° (CA change by 40°). These resultsdemonstrate that increasing the surface roughness amplifies the contactangle switching range. We attribute the change in the wettability of thesurface primarily to be due to the significant changes in its surfacemorphology or surface roughness as a result of the doping and dedopingof the conducting polymer.²³ This is clearly observed in the wide scanSEM images. For instance, a rougher and highly porous surface is seenwith the dedoped film (FIG. 18G), resulting to greater volume oftrapped-air (Cassie-Baxter model). At the same time, the surface of thededoped film contains smaller hierarchical roughness of the submicronrange (FIGS. 18D and 18E and FIG. 19). Upon doping such as theapplication of 1.05 V, the poly(thiophene) film may have possiblycollapsed and the counter ions may have occupied the pores, and thus thesurface is seen to be relatively less rough (FIG. 18F). Then upondedoping the conducting polymer such as the application of 0 V, itsmorphology with a very rough and porous surface is restored (FIG. 18G)as a result of the removal of the counter ions, and hence the filmreturns to its superhydrophobic state with water contact angle greaterthan 150° (FIG. 25A). To briefly explain the doping process, theconducting polymer will become positively charged due to the removal ofan electron from the polymer backbone upon application of a constantoxidation potential by an electrochemical methods e.g., potentiometry,and hence it will accept negatively charged counter ions (calleddopants) from the bulk solution to maintain its neutrality.^(24,25)Further, upon dedoping such as the application of a constant zeropotential, the conducting polymer will eventually return to its neutralstate, and therefore will eject the counter ions back into thesolution.^(24,25) The said doping/dedoping process was validated byX-ray Photoelectron Spectroscopy (XPS), wherein the negatively chargedcounter ion (in this case PF₆ ⁻ from the TBAH supporting electrolyte)was confirmed to be present only in the wettable polymer nanostructuredfilm state during doping as shown by the presence of the fluorine (F 1s)and phosphorus (P 2p) peaks (FIG. 25C).²⁶ The high resolution XPS scansclearly show that these unique elemental peaks (due to the dopant) arepresent only in the wetting film, but are not found in the non-wettingpolymer film state after dedoping at 0V (FIG. 26). Thus, thesuperhydrophobic property is actually observed on a non fluorinatedfilm, which is rare compared to most artificial superhydrophobicsurfaces previously reported.

The change in wettability is also accompanied by the change in theoptical property of the nanostructured film as observed by theelectrochromism of the poly(G0-3TCOOR) film (FIG. 25B, right inset). Theelectropolymerized film has a distinct orange color that changes to darkgreen upon doping. Note that the change in color of the film occursabout 1-2 seconds after applying a doping potential of 1.05 V. Similarto the wetting behavior, the switching in color from orange to darkgreen is reversible for several cycles. To understand more about thisbehavior of the conducting polymer, the same poly(G0-3TCOOR) film waselectrodeposited on ITO in order to conduct spectroelectrochemistryduring the doping and dedoping process. The poly(G0-3TCOOR) film atneutral state (dedoped) shows a λ_(max) at 440 nm (FIG. 25B), which isknown to be the π-π* transition of the poly(thiophene).²⁷ Upon doping(1.05 V), the poly(G0-3TCOOR) film depicts a broad band between 600 to800 nm range (FIG. 25B), which is due to the formation of radicalcations (called polarons).²⁸ Also, the doping is further evidenced bythe increase′ in conductivity of the poly(G0-3TCOOR). The bulkconductivity of the film is determined from the resistance using afour-point probe and thickness using a profilometry (Table II.2).

TABLE II.2 Summary of Thickness and Conductivity Measurements of theFilm Thick- Resis- ness¹ tivity² Conductivity Electropolymerized Film(nm) ohm/square) (Siemens/cm) 5 mM G0-3TCOOR on Bare Au   4-12 184.214.52-13.57 CV: 5 mM/s, 15 cycles, 0 V to 1.1 V 5 mM G0-3TCOOR on PS2.5-6.5 362.56 4.24-11.03 coated Bare Au CV: 5 mM/s, 15 cycles, 0 V to1.1 V 5 mM G0-3TCOOR on PS 2.5-6.5 166.17 9.25-24.07 coated Bare Au CV:5 mM/s, 15 cycles, 0 V to 1.1 V Apply +1.05 V, 30 mins 5 mM G0-3TCOOR onBare Au 2.5-6.5 308.18 4.99-12.98 CV: 5 mM/s, 15 cycles, 0 V to 1.1 VApply +0.85 V, 30 mins Notes: ¹Thickness measured using profilometry atdifferent areas (at least 10 areas) of the films. ²Resistivity measuredusing Four-Point Probe at different areas (at least 10 areas) of thefilms.

Upon applying a doping potential (1.05 V), the conductivity of the film(poly(G0-3TCOOR) onto 500 nm PS layer on Au) has increased to valuesbetween 9.25-24.07 S cm⁻¹ (doped) from 4.24-11.03 S cm⁻³ (dedoped film).The measured thickness of this film is in the range of 2.5 to 6.5 μm.

Referring now to FIGS. 27A-D, contact angle measurements ofpoly(G0-3TCOOR) onto 500 nm PS coated Au in (A) water before and afterspin coating of S 760P in (B) water, (C) hexadecane, and (D)diiodomethane are shown.

Finally, as an extension of this work, a facile and rapid approach ofconverting the superhydrophobic-and-superoleophilic nanostructured film(state 1) into the superhydrophilic-and-oleophobic (state 2), i.e.,completely reversing the order of wetting, was also demonstrated. Ateither states of the film, separation of oils or organic solvents fromwater or vice versa in an oil or organic solvent and water mixture usingthe film should be possible. The switching of the wettability was doneby merely spin coating a commercially available fluorinated surfactant(S 760P) as shown in FIG. 27A inset.

Clearly, the superhydrophobic-and-superoleophilic nanostructured film isinstantly converted into superhydrophilic (zero water contact angle)without further surface treatments and modifications (FIG. 27B). Also,this nanostructured film then becomes oleophobic (as opposed tosuperoleophilic prior to the surfactant treatment) since a contact angle≧90° is shown with hexadecane (FIG. 27C) and diiodomethane (FIG. 27D).The oleophobicity of the nanostructured film is not only due to thecombined effect of the hydrophobic polymer (poly(G0-3TCOOR) and presenceof the underlying PS nanoparticles (FIG. 29), but also with the presenceof the fluorinated surfactant (S 760P). The fluorinated surfactanttreatment results in a hydrophilic and oleophilic wetting behavior sincethe water and organic solvents (hexadecane and diiodomethane) contactangles of the spin coated surfactant on flat Au are 0°, ˜0°, and 33°±1,respectively. Moreover, this process of surfactant incorporation mightbe influenced by the morphology and the presence of cracking on thedoped film (FIG. 29). Current effort is underway to understand the roleof other surfactants and to develop a superoleophobic film using thesame methodology.

In conclusion, a non-flourinated superhydrophobic-and-superoleophilicpolythiophene film with simultaneous and reversible potentially-inducedwetting (switching from >150° to <60° for several cycles) andelectrochromic (switching from orange to dark green color of the surfacealso for several cycles) properties was fabricated for the first timeusing a facile and innovative approach of combining the LB-liketechnique and electropolymerization process. The fabricatednanostructured surface with unique dual wetting properties demonstratedsuperhydrophobicity at very low (<5°) and high (>70°) temperatures, verylow (pH 1) and high (pH 13) pH values, and for longer times (150 days).Furthermore, the as-prepared superhydrophobic-and-superoleophilic(state 1) nanostructured surface is also easily reversed to asuperhydrophilic-and-oleophobic (state 2) surface simply by spin coatingof a commerically available surfactant (S 760P). At either states of thesurface, separation of oils or organic solvents from water and viceversa in an oil or organic solvent and water mixture is feasible. Thus,this study may prove particularly useful in the effective removal of oiland organic solvents for water recycling. It may also find manypractical applications as coatings for anti-ice adhesion, marinecoatings, anti-corrosion, stimuli responsive surfaces such asintelligent microfluidic switches, etc. Several of these applicationsare currently being pursued by our group.

Experiments of Section II Materials

Polystyrene (PS) latex particles (2.5 wt % solids in aqueous suspension)are purchased from Polysciences, Inc. and were used without furtherpurification. Acetonitrile (ACN), sodium n-dodecyl sulfate (SDS), andtetrabutylammonium hexafluorophosphate (TBAH) were obtained fromSigma-Aldrich. The glass slides (BK 7) were acquired from VWR. The goldsurface was prepared by thermally evaporating gold (50 to 100 nm thick)under high vacuum (10⁻⁶ bar) onto a BK 7 glass slide with chromiumadhesion layer (˜10 nm thick). The Cr and Au depositions were done at arate ˜0.4 Å sec⁻¹ and 1.1 Å sec⁻¹, respectively, using a thermalevaporator (Edwards). The deionized water (resistivity ˜18 mΩ·cm) usedfor the dilution of PS particles was purified by a Milli-Q Academic®system (Millipore Cooperation) with a 0.22 micron Millistack filter atthe outlet. The fluorinated surfactants (S 760P) were obtained fromChemguard, Inc. The monomers used in the electrochemical polymerizationwere synthesized in our laboratory. And the details of the synthesis ofethyl 2-(2,5-di(thiophen-2-yl)thiophen-3-yl)acetate (Monomer 1, G03TCOORwhere R═CH₂CH₃), and 2-(2,5-di(thiophen-2-yl)thiophen-3-yl)acetic acid(Monomer 2, G03TCOOH) are described below (Scheme II.1).

Synthesis of the Monomers Synthesis of ethyl2-(2,5-di(thiophen-2-yl)thiophen-3-yl)acetate (G03TCOOR, where R═CH₂CH₃)

The synthesis of G03TCOOR was carried out by first synthesizing ethyl2-(2,5-dibromothiophen-3-yl)acetate as reported in the literature.³⁰ ¹HNMR (CDCl₃): 6.94 (s, 1H), 4.17 (q, 2H, J=7.15 Hz), 3.55 (s, 2H), 1.27(t, 4H, J=7.14 Hz) as shown in FIG. 28.

The procedure described by Taranekar et al³⁰ was modified to synthesizeG03TCOOR. Ethyl 2-(2,5-dibromothiophen-3-yl)acetate (6.4 g, 10 mmol) and2-(tributylstannyl) thiophene (15 g, 20 mmol) were added to a 30 mL drydimethylformamide (DMF) solution ofdichlorobis(triphenylphosphine)palladium (Pd(dpp)Cl₂) (1.3 g, 1.5 mmol).After three freeze thaw cycles, the mixture was heated at 100° C. for 48hr. The mixture was cooled to room temperature and poured into a beakercontaining 150 mL of water and subsequently extracted with CH₂Cl₂. Theextracted CH₂Cl₂ mixture was dried with Na₂SO₄. After filtration andevaporation of the solvent, the crude product was purified bychromatography on silica gel using toluene as an eluent. The finalproduct was obtained in 85% yield as pale yellow oil. Thecharacterization of the compound was found in accordance with theliterature.¹ ¹H NMR (CDCl₃): δ 6.8-7.2 (m, 7H), 4.19 (q, 2H, J=7.15 Hz),3.72 (s, 2H), 1.27 (t, 4H, J=7.14 Hz) as shown in FIG. 29.

A total of 4 g of G03TCOOR was dissolved in methanol and added to a 20%aqueous sodium hydroxide solution (200 mL) The mixture was then refluxedfor 4 hr. After removal of methanol, the aqueous solution was washedwith ether, acidified with concentrated HCl to pH 1.0 and extracted byether. The ether solution was washed several times with water andevaporation of ether yielded 3.4 g G03TCOOH. The characterization of thecompound was found in accordance with the literature² as shown FIG. 30.

Instrumentation

Electrochemistry

Cyclic voltammetry was performed in a fabricated electrochemical cell(Teflon-made, with a diameter of 1.0 cm and volume of 0.785 cm³) using aconventional three-electrode cell using an Autolab PGSTAT 12potentiostat (MetrOhm, USA). The potentiostat is controlled by GPESsoftware (version 4.9).

Static and Dynamic Contact Angle

The static contact angle measurements were done using a CAM 200 opticalcontact angle meter (KSV Instruments Ltd) with CAM 200 software. Theexperiment was carried out by slowly moving upward the sample stage withthe sample on top to come into contact with the liquid droplet (˜1 μL)that was suspended at the tip of the micro syringe (200 μL). When usingwater for contact angle measurements for the superhydrophobic surface,the sample was only brought at a distance of few millimeters below thewater droplet, and then the droplet was carefully released to thesurface. Unlike the other solvents, the water droplet will not adsorb orfall from the tip of the needle when in contact with the as-preparedsuperhydrophobic surface of poly(G0-3TCOOR)/PS (500 nm size) coatedsubstrate. The reading of the contact angle was done after 30 secondswhen the droplet has been made into the surface, and at least threetrials were performed at various positions of the nanostructuredsurface. The solvents used for contact angle measurements were Milli-Qwater, hexadecane and diiodomethane. For dynamic contact anglemeasurements, the angles were measured using a Ramé-Hart model 100contact angle goniometer. The liquids were dispensed and withdrawn usinga Matrix Technologies micro-Electrapette 25. Contact angles werecollected and averaged from measurements on four distinct slides usingthree separate drops per slide. FIG. 31 shows the results of the staticcontact angle measurements.

Profilometry

The thickness of the nanostructured films was acquired by surfaceprofilometry using the Alpha-Step 200 profilometer. The Alpha-Step 200accurately measures surface profiles below 200 Å and up to 200 μm. A lowstylus force of 5 mg was used during the scanning to avoid damaging orscratching the polymer surface. The measurements were done at least 10times on different areas of the film under ambient and dry conditions.

Atomic Force Microscopy (AFM)

AFM analysis was carried out in a piezo scanner from AgilentTechnologies. The scanning rate was between 0.8-1.5 lines/s.Commercially available tapping mode tips (TAP300, Silicon AFM Probes,Ted Pella, Inc.) were used on cantilevers with a resonance frequency inthe range of 290-410 kHz. The scanning of the PS coated Au and ITO wasperformed under ambient and dry conditions. All AFM topographic images(AAC tapping mode) were filtered and analyzed by using Gwyddion software(version 2.19). Note: Only the PS coated substrates were scanned in theAFM. Because of the formation of very rough surfaces, theelectropolymerized films on PS coated substrates were then scanned inthe SEM.

Four-Point-Probe

The conductivity measurements were determined with a four point probetechnique using the Keithley 2700 Multimeter Intergra Series. All filmswere measured at least five times on different area under ambient anddry conditions.

Attenuated Total Reflectance Fourier Transform Infrared (ATR-FTIR)

The ATR FTIR spectra were obtained on a Digilab FTS 7000 equipped with aHgCdTe detector from 4000 to 600 (cm-1) wavenumbers. All spectra weretaken with a nominal spectral resolution of 4 cm⁻¹ in absorbance mode.All films were measured under ambient and dry conditions.

FTIR Imaging

FT-IR imaging was performed on a Digilab Stingray imaging systemconsisting of a Digilab FTS 7000 spectrometer, a UMA 600 microscope, anda 32×32 mercury-cadmium-telluride IR imaging focal plane array (MCT-FPA)image detector with an average spatial area of 176 μm×176 μmintransmission mode. An 8 cm⁻¹ nominal spectral resolution and an undersampling ratio (UDR) of 4 for the imaging were set up, and the spectraldata were collected with 1240 scans. All image processing and dataextraction were obtained using the Win-IR Pro 3.4 software package.

Scanning Electron Microscopy

The morphology of the samples was examined by field emission scanningelectron microscopy (FE-SEM) using a JSM 6330F JEOL instrument operatingat 15 kV. Prior to SEM analysis, the films were thoroughly dried undervacuum for at least 24 hrs.

Instrumentation and Analysis

CV was performed in a fabricated electrochemical cell (Teflon-made, witha diameter of 1.0 cm and volume of 0.785 cm³) using a conventionalthree-electrode cell using an Autolab PGSTAT 12 potentiostat (MetroOhm,Inc). AFM measurements were done on a PicoScan 2500 AFM from AgilentTechnologies using tapping mode with scanning rate between 1-1.5lines/s. Commercially available tapping mode tips (TAP300-10, siliconAFM probes, Tap 300, Ted Pella, Inc) were used on cantilevers with aresonant frequency in the range of 290-410 kHz. All AFM topographicimages were filtered and analyzed using the Gwyddion software (version2.19). Static water contact angle (WCA) measurements were accomplishedon a CAM 200 optical contact angle meter (KSV Instruments Ltd). Notethat the WCA value was acquired only when the water droplet was droppedat a relatively far distance (ca 0.3 cm) away from the surface since noreading can be measured if the droplet is to come into contact with thesubstrate. For dynamic contact angle measurements, the angles weremeasured using a Ramé-Hart model 100 contact angle goniometer. Theliquids were dispensed and withdrawn using a Matrix Technologiesmicro-Electrapette 25. Contact angles were collected and averaged frommeasurements on four distinct slides using three separate drops perslide. XPS measurement (at take off angle of 45° from the surface) werecarried out on a PHI 5700 X-ray photoelectron spectrometer with amonochromatic Al Ka X-ray source (hn=1486.7 eV) incident at 90° relativeto the axis of a hemispherical energy analyzer. The ATR IR spectra ofthe film on Au and ITO substrate were obtained on a Digilab FTS 7000equipped with a HgCdTe detector from 4000 to 600 (cm⁻¹) wavenumbers witha nominal spectral resolution of 4 cm⁻¹ in absorbance mode. FT-IRimaging was performed on a Digilab Stingray imaging system consisting ofa Digilab FTS 7000 spectrometer, a UMA 600 microscope, and a 32×32mercury-cadmium-telluride IR imaging focal plane array (MCT-FPA) imagedetector with an average spatial area of 176 μm×176 μm in transmissionmode. SEM analysis was done in field emission scanning electronmicroscopy (FE-SEM) using a JSM 6330F JEOL instrument operating at 15kV. Profilometry of model Alpha-Step 200 was used to measure thethickness of the polymeric surface. A low stylus force of 5 mg was usedduring the scanning to avoid damaging the polymer surface. Theconductivity measurements were determined with a four point probetechnique using the Keithley 2700 Multimeter Intergra Series. Completedetails about the instrumentation are found in the supporting document.

Film Preparation

The superhydrophobic-and-superoleophilic conducting surface wasfabricated by simple two-step process such as (1) layering of PS latexmicrobeads onto conducting substrates like Au and ITO slides, and (2)electropolymerization of the monomer into the PS-coated slides. Thelayering of PS latex beads was prepared using a similar proceduredescribed earlier by Grady and co-workers.¹⁴ The substrate was attachedvertically into the dipper motor via a Teflon clip and was dipped into asolution of PS particles (1 wt % in Milli-Q water) and SDS (34.7 mM) asspreading agent. The substrate was then withdrawn vertically from thesolution at a lift-up rate of 0.1-0.3 mm/s. The substrate was then driedby suspending it in air for a few min. After the layering of the latexspheres, the monomer (5 mM G0-3TCOOR in ACN with 0.1 M TBAH assupporting electrolyte) was electropolymerized onto the PS-coatedsubstrate (Au or ITO) as the working electrode in a standard threeelectrode measuring cell with platinum (Pt) wire as the counterelectrode and Ag/AgCl wire as the reference electrode. Theelectropolymerization was done using CV technique in a fabricatedelectrochemical cell (Teflon made). The potential was scanned between 0V to 1.1 V (and also 0V to 1.5 V) for 15 cycles at a scan rate of 5mV/s. Note that the use of very slow scan rate will result to theformation of thicker polymer coatings. Also, it is also possible to dothis deposition of polymer by chronoamperometric or potentiostaticmethods. After electrodeposition, the film was thoroughly washed in ACN(at least 3 times) to remove the excess monomer and loosely adsorbedpolymer or oligomer, and a monomer free scan (in a solution of ACN with0.1 M TBAH as supporting electrolyte) was performed by using exactly thesame electrochemistry set-up (FIG. 15A) and settings but for 1 CV cycleonly. Finally, the electropolymerized film was thoroughly dried invacuum for at least 1 hr prior to any characterizations. To perform thedoping and dedoping of the conducting polymer, a constant potential wasapplied to the film when it is immersed into the ACN with the supportingelectrolyte (0.1 M TBAH). The same electrochemistry set-up on FIG. 15Awith the three electrode system (electropolymerized colloidally templatesubstrate as working electrode, Pt wire as counter electrode, andAg/AgCl wire as reference electrode) was used for the application of theconstant potential of 0V (dedoping) and 1.05 V (doping). A normal beakerinstead of the fabricated electrochemistry cell can also be used to dothe experiment. To convert the superhydrophobic-and-superoleophilicnanostructured film into superhydrophilic-and-oleophobic as an extensionwork, a fluorinated surfactant (S 760P) was spin coated on top of thefilm. The spin coating was done 2 times at 4000 rpm for 120 sec followedby drying the film in vacuum for at 1 hr.

Surfactant Information on S760P

It is a class of commercially available perfluoro derivatives withCAS#s. It is a mixture of these two: CAS 65530-72-5 has a chemical nameof Poly(difluoromethylene), alpha-fluoro-omega-(2-(phosphonooxy)ethyl)-,diammonium salt. CAS 65530-70-3 has a chemical name ofPoly(difluoromethylene),|alpha-fluoro-|omega-(2-((2-methyl-1-oxo-2-propenyl)oxy)ethyl).

We also used a mixture of PFOA=perfluorooctanoic acid andDCC=dicyclohexylcarbodiimide, but did not report the results here. Italso worked, but not as hydrophilic as the first two. In which case, wesee that the mixture of any of these perfluorinated surfactants or itsclass will give different degrees of reversibility of wetting behavior.

REFERENCE CITED IN SECTION II

The following references were cite in the section of the specification:

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Detailed Description of Section III Tunable Protein and Bacterial CellAdsorption on Colloidally-Templated Superhydrophobic Polythiophene FilmsSummary of the Invention Section III

A facile approach for enabling or inhibiting the adsorption of proteinand adhesion of bacterial cells on a potential-induced reversiblywettable polythiophene film is described. The superhydrophobic polymericsurface was first prepared by a two-step process that combines thelayering of polystyrene (PS) latex particles via a Langmuir-Blodgett(LB)-like technique followed by Cyclic Voltammetric(CV)-electrodeposition of polythiophene from a terthiophene estermonomer. The polythiophene conducting polymer coating enabled control ofthe wettability of the surface by simply changing its redox property viapotential switching. The influence of morphology on this switchingbehavior is also described. The wettability in return controls theadsorption of protein and adhesion of bacterial cells. For instance, theundoped polythiophene film, which is superhydrophobic, inhibits theadhesion of fibrinogen proteins and Escherichia coli (E. coli) cells. Onthe other hand, the doped film, which is hydrophilic, leads to increasedattachment of both protein and bacteria. Unlike most syntheticanti-wetting surfaces, the as-prepared superhydrophobic coating isnon-fluorinated. It maintains its superhydrophobic property at a widerange of pH (pH 1-13) and temperature (below −10° C. and between 4° C.and 80° C.). Moreover, the surface demonstrated self-cleaning propertiesat a sliding angle as low as 3°±1. The proposed methodology and materialshould find application in the preparation of smart or tunablebiomaterial surfaces that can be either resistant or susceptible toproteins and bacterial cell adhesion by a simple potential switching.

Introduction Section III

The phenomenon of superhydrophobicity and the preparation of syntheticsuperhydrophobic surfaces have recently attracted much attention due toits potential industrial and biomedical applications.¹ The design ofartificial anti-wetting surfaces is nature inspired. For instance, thenatural superhydrophobic surfaces, which are found in many plant leaveslike the Lotus leaf,² the Lady's Mantle,³ and in many insects⁴ like thewater strider, butterfly, and the cicada, contain hierarchical roughnessthat has been mimicked in hydrophobic materials. Ma and Hill⁵ summarizedthe different materials and the common strategies utilized forstructuring the surface to template the natural design. Most of thesemethods include tedious lithographic steps and require intricateinstrumental set-up, which can limit their realistic application forsurface coatings. Although not widely reported, electrochemicalpolymerization or electrodeposition of polymers can be an alternativefor making superhydrophobic surfaces.⁶ However, most of the reports onelectrodeposition of π-conjugated polymers for anti-wetting purposes usefluorinated substituents, which are not only more expensive butbio-accumulates in the environment.⁷ Therefore, these concernsnecessitate the search for non-fluorinated π-conjugated polymeralternatives. Among the π-conjugated polymers, poly(thiophenes) and itsderivatives are well-known and are relatively stable for practicalapplications.⁸

Despite the numerous and successful bio-mimetic efforts to achievesuperhydrophobic surfaces,^(5,6) there are only few studies oninvestigating their potential for biomaterial applications. Genzer andEfimenko⁹ reported recent developments on superhydrophobic coatings andnoted the limited work on their applications to prevent biofouling onsurfaces or on biomedical devices.¹⁰ The resistance as well as theadsorption of protein or bacteria to material surfaces can have diversemedical, industrial, and environmental applications and implications.For instance, the adsorption of protein to surfaces is important to thedevelopment of biosensors and immunoassays.¹¹ Materials like di-blockcopolymers that are physically or chemically adsorbed to the surfacehave been used for controlling the adhesion of proteins.¹² In the caseof bacterial adhesion to surfaces and biofilm formation, these phenomenacan help in the degradation of organic matter in wastewater treatment,¹³bioremediation,¹⁴ selective extraction of metals from ores,¹⁵ and onbasic studies for in vitro growth of bacterial cells. On the other hand,the adhesion of proteins or bacteria can cause impairment of the surfacefunctionality of biomedical devices¹⁶ such as of catheters,¹⁷implants,¹⁸ and artificial organs.^(17a,19) Furthermore, adhesion ofbacteria on the water distribution system can clog pipes and generatecorrosion.^(20,21) Therefore, numerous efforts have been directed tomodify the surface with a material that would resist bacterialadsorption and colonization, as well as adsorption of proteins.²² Onepossible approach to prevent biofouling is to make the surfacesuperhydrophobic, i.e. by controlling the surface energy and surfacetopography of the substrate.²³ Marmur²⁴ claimed that biofoulinghindrance can be obtained by minimizing the contact between water andsurface using a superhydrophobic coating, since foulers are generallybiological materials suspended in water with high affinity forhydrophilic surfaces. Moreover, Rubner et al.²⁵ underscored thatsuperhydrophobic surfaces can actually provide resistance or reducedcapacity of bacteria to achieve stage I and/or stage II in bacterialadhesion.

Since material surfaces that control adhesion of protein and bacteriacells are medically, industrially, and environmentally relevant, it willbe interesting to create a tunable surface that can also facilitateself-cleaning So far, most reports have focused only on making a surfacethat is either resistant or susceptible to protein or bacteria adhesionbut not tunable. In the present work, we developed a facile approach toenable controlled adhesion of proteins and bacterial cells to surfaces.These surfaces are coated with highly stable and albeit nonfluorinatedelectrodeposited superhydrophobic polythiophene, utilizing a colloidaltemplate-assisted electropolymerization technique. This study alsoprovides an insight on controlling the wettability of the surface by asimple potential switching of the redox property of the conductingpolymer surface. Finally, the effect of changing the redox property ofthe polymeric surface was explored with the adsorption or inhibition offibrinogen and E. coli attachment to the surfaces. To the best of ourknowledge, this is one of the first reports on controlled attachment andprevention of protein and bacteria adhesion utilizing apotential-induced and reversibly-wettable polythiophene film. Theadvantage of using a conducting polymer coating is the ability tocontrol the wettability and electro-optical properties of the polymericsurface simultaneously by simply changing its redox property, i.e.,enabling self-cleaning function by an ex-situ change in potential.Recently, we have demonstrated the effect of altering the redox propertyof polythiophene film that is electrodeposited on flat surfaces tofacilitate the effective release of drug molecules from an ultrathinfilm of molecularly imprinted polythiophene surface.²⁶

Results and Discussion Section III Film Preparation and Characterization

The anti-wetting surface was fabricated using a two-step approach. FIG.32 depicts the schematic representation of the film fabrication startingwith the colloidal template (PS particle) layering onto a planarconducting substrate by a Langmuir-Blodgett (LB)-like technique.²⁷ Thismethod was used because it allows two dimensional (2D) monolayer andclosely-packed ordering of particles on flat surfaces, which isdependent on the vertical lifting speed of the substrate and colloidalparticle and surfactant concentrations.²⁷ FIGS. 33A-D displays theatomic force microscopy (AFM) topography 2D (FIG. 33A) and 3D (FIG. 33B)images of the single layer 500 nm sized PS particles adsorbed on Ausubstrate and the scanning electron microscopy (SEM) images afterpolythiophene electrodeposition (FIG. 33C and 33D) of the doped andundoped films, respectively. The AFM images reveal a highly orderedmonolayer assembly of colloidal particles in hexagonal packing orhoneycomb arrangement as clearly seen in the high magnification image(inset of FIG. 33A). Similar surface patterns were also observed forother sizes of PS when the deposition was done on an Indium Tin Oxide(ITO) substrate (FIGS. 34A-D). Attenuated total reflection infrared (ATRIR) spectrum of the PS layer on Au is presented in FIG. 34D, which showsthe signature peaks of PS, confirming its presence on the surface.

Electrodeposition of the polythiophene layer on the PS-coated conductingsubstrate was performed by CV technique. This method allows directgrafting of the conducting polymer onto the electrode surface, controlof polymer film thickness, surface growth, and morphology by varyingvarious set-up parameters such as scan rate, CV cycles, and potentialwindow.²⁸ The morphology by SEM imaging is shown in FIGS. 33C and 33Dfor the doped and dedoped films, respectively. Further discussion onmorphology vis-à-vis wetting properties is elaborated on the succeedingsections. FIG. 35A presents the typical CV diagram of the anodicelectropolymerization of the (ethyl2-(2,5-di(thiophen-2-yl)thiophen-3-yl)acetate (G0-3TCOOR) monomer.²⁹ Theadvantage of using the terthiophene monomer for electropolymerization isthe lower oxidation potential compared to its mono or bithiophenecounterparts.³⁰ This process is evidenced by the increasing current inthe oxidation (between 0.8 V to 1.1 V) and reduction (between 0.6 V to1.0 V) peaks until the 15^(th) cycle (FIG. 35A), which is attributed tothe linking of the terthiophene units and electrodeposition of thematerial onto the electrode substrate.²⁹ The current increase in theanodic scan that occurs from the 2^(nd) cycle with an onset potential of˜0.6 V is attributed to the oxidation of the more conjugated species.²⁹The deposition of the polymer film onto the electrode substrate wasconfirmed by the appearance of the same redox couple in the monomer-freepost-polymerization scan (inset of FIG. 35A). During theelectropolymerization, a very slow scan rate (5 mV/s) was applied toenable deposition of a thicker polymer film on top of thecolloidally-templated electrode substrate. A film thickness between 2.5to 6.5 μm was determined from profilometry measurements.

The electrodeposition of the conducting polymer onto the PS-coatedsubstrate was verified by X-ray photoelectron spectroscopy (XPS). Thesurvey scan (FIG. 35B) exhibits the expected elemental composition forpoly(G0-3TCOOR) such as carbon (C), oxygen (O), and sulfur (S)atoms.^(26a) The S 2p peak (inset of FIG. 35B) in the high resolutionscan at the range of 162-165 eV is a signature peak forpolythiophene,^(26a) which is due to the sulfur atom of the thiophenering.

Testing for Superhydrophobicity and Self-Cleaning Effect

The wettability of the poly(G0-3TCOOR)/PS surface was evaluated. Thesurface exhibited a static water contact angle (WCA) value of 154°±1(FIG. 36A) at ambient conditions, which is attributed to the synergesticeffect of the combined heirarchical roughness, which is seen in thescanning electron microscopy (SEM) images, and the presence of thehydrophobic conducting polymer coating on the surface. To underscore theimportance of the PS template underlayer array, the poly(G0-3TCOOR) filmwas electrodeposited using the same CV condition on a flat surface, andthe contact angle was also measured, which showed a value of only103°±1. This result shows the importance of the 500 nm sized PS templatearray underlayer to give a superhydrophobic effect on the surface. ThePS monolayer array actually provides an initial sub-micron scaleroughness to enhance the hydrophobicity of the surface.

The structuring of the surface was determined by SEM analysis. The SEMimaging (FIG. 36) displayed an irregularly rough surface of theas-prepared superhydrophobic film. This complex surface morphology wasexpected because the electropolymerization was done in a non-planar 2Dsubstrate with a very slow scan rate. Based from the SEM lowmagnification image (FIG. 36B), the irregular roughness on the surfaceshows hierarchy or stepping order, which can serve as a multiple barrierfor resisting the adhesion of water to the surface. For instance, thetopmost layer comprises mainly of highly porous foam-like features thatare above the micron scale bumps with size much greater than the PSparticle. In some regions, highly dense foam-like structures of theconducting polymer are also seen on the surface (FIG. 36C). Theunderlayer (at low region below the foam-like features) clearly showsthe continuous honeycomb assembly of the PS particle that is smearedwith nanometer-sized asperities due to the conducting polymer (FIG.36D). This result proves that the superhydrophobicity is not necessarilydependent on the regularity of the surface roughness like the surface ofthe Lotus leaf² and many other synthetic analogues prepared bysophisticated lithographic techniques, but by the presence ofhierarchical features contributing to the non-wetting phenomenon⁵ whichis essentially a Cassie-Baxter Model.³³

These films showed superior temperature and pH stability. Thesuperhydrophobicity of the poly(G0-3TCOOR)/PS surface was tested atvarious water droplet temperatures ranging from 4° C. to 80° C. It wasobserved that the surface remained superhydrophobic (WCA≧150°) at allmeasured temperatures (FIG. 37A). Furthermore, the superhydrophobicitywas maintained even when the surface was incubated at below freezingcondition (−10° C.) for 1 and 4 days giving WCA values of 152°±3 and153°±2, respectively. The surface also maintained itssuperhydrophobicity at a wide pH range (pH 1-13) (FIG. 37B). The highwater repellency of the same surface that is preserved at very low andvery high pH values and at low and high temperatures of water is unusualand is not easily achieved in many synthetic superhydrophobic surfaces.

The static contact angle analysis was validated by dynamic measurementthat displayed a high advancing (θ_(adv)) and receding (θ_(rec)) watercontact angle values of 154°±1 and 151°±1, respectively. The differencein the two values is the contact angle hysteresis,³¹ which is also usedto gauge on whether the superhydrophobic surface will demonstrate thesliding of the water droplet.^(1b,32) Since the superhydrophobic surfacehas a very low hysteresis of <5°, it will most likely exhibit therolling of the water droplet akin to the Lotus leaf.^(1a,32a)

The self-cleaning property of the as-prepared superhydrophobicpolythiophene surface was confirmed, which allowed the rolling of thewater droplet at the sliding angle of 3°±1. FIG. 37C displays images ofthe water droplet, hanging at the tip of the needle and at the same timetouching the polymeric surface on the other side, displaying its abilityto move freely across the superhydrophobic surface. These images vividlyreveal that the surface is highly repellent to water. Because the waterdroplet was able to roll freely on the surface at a very low slidingangle, the superhydrophobic surface is characterized by theCassie-Baxter model,^(32a,33) which explains that the water droplet issitting and not pinned above the composite surface of the solidprotuberances and air (described as heterogeneous wetting regime³⁴).With the high porosity of the actual surface, as determined from the SEManalysis, the superhydrophobic surface is believed to entrap more air,particularly onto the micron scale asperities (FIG. 36B) and foam-likestructures (FIG. 36C), and thus creating a liquid-gas layer upon contactwith water, which is likely the reason for the sliding of the waterdroplet across the anti-wetting surface. FIG. 37D (top left) shows theimage of the pristine superhydrophobic coating electrodeposited on ITO,while FIG. 37D (bottom left) displays the image of the same but dustedsurface after rolling the water droplet. Clearly, it is shown that thedust particles are completely removed and picked up by the water dropletthat rolled off the surface, and hence the superhydrophobic surface hasbeen proven to be self-cleaning.

Switchable Surface Wettability

The redox property of the cross-linked conducting polymer film wasinvestigated by applying a constant oxidation potential of 1.05 V usingthe same three electrode system in a monomer free condition. The appliedvoltage was determined from the peak potential of the CV diagram (FIG.35A) in the anodic scan during the electropolymerization of theterthiophene monomer. Previously, our group has investigated the redoxproperty of the conducting polymers of polycarbazole and polythiopheneusing in-situ measurements.³⁵ However, the surface wettability of theelectrodeposited conducting polymers was not studied. In order toexamine the change in the redox property of the polymer film, theelectrodeposition of the conducting polymer was done in a transparentconducting substrate like ITO such that UV-Vis measurements can beperformed. Prior to the application of the constant positive potential,the UV spectrum shows a maximum absorption peak (λ_(max)) at 440 nm,which is known as the π-π* transistion of the polythiophene film (uppercurve of FIG. 38A).³⁶ At this condition of the film, the conductingpolymer is considered to be neutral or undoped. Then after applying apotential of 1.05 V to the electrodeposited film, the spectrum displaysa new broad peak between 600 to 800 nm (FIG. 38A bottom curve), which isdue to the formation of polarons³⁷ of the conjugated polythiophenespecies and their complex redox ion couple with hexafluorophosphate ions(PF₆ ⁻). During the application of the oxidation potential, theconducting polymer is known to become positively charged, and thusaccepts the negatively charged counter ions (called dopants) from thesupporting electrolyte in the bulk solution to maintain its neutralityand this process is referred as electrochemical doping.³⁸ As determinedfrom the contact angle (inset of FIG. 38A), the doping of thepoly(G0-3TCOOR) on PS coated substrate instigated the change in thewettability of the surface, which is attributed to the change in surfacemorphology and the effect of the dopant.³⁹ The change in surfacemorphology is evident in FIGS. 33C and 33D over wide scan areas. Forinstance, a rougher and highly porous surface is seen with the dedopedfilm (FIG. 33D and FIG. 36B-D), resulting to greater volume oftrapped-air (Cassie-Baxter model³³). At the same time, the surface ofthe dedoped film contains smaller hierarchical roughness of thesubmicron range (FIGS. 36B and 36D). Upon doping such as the applicationof 1.05 V, the polythiophene film may have possibly collapsed and thecounter ions may have occupied the pores, and thus the surface is seento be relatively less rough (FIG. 33C). Then upon dedoping theconducting polymer such as the application of 0 V, its morphology with avery rough and porous surface is restored (FIG. 33D). During thededoping process, the polymer film is believed to eject the counter ionback into the bulk solution and returns to its neutral state,³⁸ which isproven by the appearance of the same UV spectrum with only oneabsorption peak maximum at 440 nm. The application of the oxidationpotential of 1.05 V has easily converted the superhydrophobic surface(WCA≧150°) into hydrophilic surface with WCA of ˜60°. Then upon dedopingthe same surface, the polythiophene film is switched back tosuperhydrophobic state with a WCA equivalent to 152°±1. Thereversibility of the surface wettability and color of thecolloidally-templated polythiophene film via potential switching between0 V and 1.05 V is shown in FIG. 39. Note that the reversible change inwetting (superhydrophobic to hydrophilic and back) with simultaneouschange in color or electrochromism (orange to dark green and back) isalso a unique aspect of these films. Based from these results, thepoly(G0-3TCOOR)/PS surface can be considered as a stimuli responsivematerial.

The doping/dedoping of the polythiophene was further confirmed by XPSmeasurements. The high resolution XPS scans display the flourine (F 1s)peak (FIG. 38B) between 682-688 eV and phosphorus (P 2p) peak (FIG. 38C)between 133 to 137 eV in the doped polymer surface, which are due to thePF₆ ⁻ (counter ion from the supporting electrolyte, TBAH). These peakswere not present upon dedoping of the same polymeric surface. Theappearance of these unique elemental markers, which are due only to thecounter ion, verifies the electrochemical doping of the electrodepositedconducting polymer. Interestingly, it is the absence of the fluorinepeak (from TBAH dopant) that facilitates superhydrophobicity for thisfilm. The sulfur peak (S 2p), which is the signature peak of thepolythiophene, was also scanned in the XPS before and after doping tocheck for the stability of the conducting polymer. The presence of the S2p peak (FIG. 40) at the same position and similar intensity signifiesthat the conducting polymer is highly stable and is not impaired by theelectrochemical doping at the present condition.

Protein Adsorption Studies

The fabricated superhydrophobic surface was then tested for proteinadsorption using fibrinogen protein as a model, which is a plasmaprotein present in relatively large quantities in the blood (0.2-0.4%),and plays a vital role in clot formation. This plasma protein has a sizeof 340 kDa and is commonly used to evaluate the biocompatibility orthrombogenesis of material surfaces, since it is known to absorb to mostmaterial surfaces.⁴⁰

To determine the amount of protein adsorbed onto the electropolymerizedcolloidally-templated surface, quartz crystal microbalance (QCM) wasused. The Sauerbrey equation was used to quantify the amount offibrinogen adsorbed on different surfaces:

$\begin{matrix}{{\Delta \; F} = \frac{{- 2}F_{q}^{2}\Delta \; m}{A\sqrt{\rho_{q}\mu_{q}}}} & \left( {{III}{.2}} \right)\end{matrix}$

where ΔF 1s the change in frequency in Hz, m is the mass change in g,F_(q) (=5 MHz) is the resonant frequency of the QCM crystal, A (=1.37cm²) is the area of the electrode, ρ_(q) (=2.65 g/cm³) is the density ofthe quartz, and μ_(q) (=2.95×10⁶ N cm⁻²) is the shear modulus of thequartz. The negative sign in the formula denotes that the film is beingadsorbed onto the QCM crystal. By substituting all the abovementionedvalues into the Equation III.2, the change in mass (Δm in units of g)can be easily calculated using the simplified equation:

Δm=−2.40×10⁻⁸DF  (III.3)

The results are summarized in Table III.1.

TABLE III.1 Summary of the Qcm Measurements in Air of FibrinogenAdsorption on Different Surfaces ΔF Ave. Mass Density* Substrate (Hz)(μg · cm²) 1. Poly(G0-3TCOOR)/PS Au, −99.64 1.75 Undoped Film 2.Poly(G0-3TCOOR)/PS Au, −565.01 9.90 Doped Film 3. Bare Au −308.29 5.404. Poly(G0-3TCOOR)/PS Au, −101.1 1.77 Undoped Film Injection of PBSsolution only (control) *Calculated using the Sauerbrey equation(Equation III.2).

The undoped poly(G0-3TCOOR)/PS Au surface, which was determined to besuperhydrophobic, had the least change in delta frequency (ΔF). Itsmeasured value was similar to the ΔF when a PBS solution was injectedinto the same surface (control experiment). Furthermore, a positivecontrol experiment was also done by simply injecting the same proteininto the unmodified Au substrate. As expected, a higher change in ΔF wasobtained, which is possibly due to the non-specific adsorption ofprotein. This finding implies that the undoped surface is highlyresistant to the adsorption of fibrinogen. The change in the ΔF (˜100Hz) upon injection of the buffer to the undoped surface is attributed tothe possible intake of PBS ions or water molecules into the surface.This is possible since the surface is highly porous as observed in theSEM (FIG. 36). Moreover, the N₂ drying after protein incubation may notbe enough to completely dry the surface. However, upon doping the samesurface, it allowed the adsorption of more protein with a significantdecrease in the change in frequency (ΔF) by more than seven-fold. Thisresult indicates that the same surface can be switched from inhibitoryto adsorptive for proteins by simply doping/dedoping the polymericsurface, and thus potentially useful for making smart or tunable filmsthat are stimuli responsive.

The QCM measurements in dry state was also validated by the analysis insolution (FIG. 41) that showed the same trend with the least andsignificant change in ΔF in the undoped superhydrophobic and in thedoped surfaces, respectively. Also, the adsorption of fibrinogen ontothe electrodeposited poly(G0-3TCOOR) on bare Au was measured, and thebinding curve is shown in FIG. 42 that shows relatively proteinadsorption resistancy of the surface as compared to the unmodified Ausurface. The differences in the ΔF value between the QCM measurements indry state and in solution can be credited to the effect of washing step(injection of milli-Q water to minimize/remove the salts) or N₂ dryingafter incubation with the protein solution.

The results of the QCM measurements were further verified by contactangle, ATR IR, and XPS analyses. From the static contact angle, theundoped polymeric surface remains superhydrophobic (WCA≧150°) even afterincubation in the protein solution for ˜950 minutes (FIG. 43A-top row),which means that the surface is highly repellent to fibrinogen over longperiods of time. However, upon doping the same surface and incubatingwith a protein solution, the contact angle increased from 58°±1 to 96°±6(FIG. 43A-bottom row), due to fibrinogen adsorption. The increased incontact angle is expected since the adsorbed fibrinogen will expose itshydrophobic domains in air.⁴¹ The result of the contact angle wascorroborated with the results of the ATR IR analysis (FIG. 43B). Theundoped polymeric surface has shown similar IR spectrum even afterdipping it in the protein solution. However, after doping the polymericsurface and immersing into a fibrinogen solution, the spectrum of thedoped surface showed new peaks in the range of 3100-3600 cm⁻¹,attributed to the OH and NH stretching vibrations⁴² from the protein.⁴¹Based on previous reports, the NH stretch correspond mostly to thelysine and arginine side groups of the αC domain of fibrinogen.⁴¹ Tofurther confirm that the protein is really adsorbed onto the dopedpolymeric surface, XPS analysis was also performed. The wide XPS scan(FIG. 43C) reveals a strong N 1s peak at 400 eV, which is an elementalmarker for the fibrinogen proteins. This element is not present in thecolloidally-templated electrodeposited polythiophene. A high resolutionscan of the nitrogen element (inset of FIG. 43C) was also performed toverify the result. As expected, a prominent N is signal appears between398-402 eV. Therefore, these results support that fibrinogen hasadsorbed onto the doped polymeric surface.

The resistance to protein adsorption onto the undoped polymeric surfacecan be explained by the fact that superhydrophobic surfaces preventattachment of the biofouler dissolved in aqueous solution,²⁴ i.e., thecontact between water and surface is minimized possibly due to theformation of the gas-liquid interface^(32a,33) with the multi-scalestructuring.^(10b) On the other hand, the adhesion of fibrinogen ontothe doped polymeric surface can be ascribed to the increased contactbetween the aqueous media that contains the protein and the hydrophilicsurface. Moreover, the adsorption of protein can also be related to theelectrostatic interaction between the positively charged surface and thenegatively charged protein. Note that fibrinogen has an isoelectricpoint of 5.5 and have a net negative charge in PBS buffer at pH 7.4.⁴³Our results are consistent with the earlier findings of Chen andco-workers^(1c) that their oxygen plasma treated Teflon superhydrophobicsurface resisted the adsorption of protein similar to a PEG surface.However, upon switching the same surface into wettable state (morehydrophilic) by charging with an electric field, it promoted theadhesion of protein.

Bacteria Adhesion Studies

The ability of the surfaces to inhibit bacterial attachment was testedby incubating the films with the model bacteria E. coli for 2 h. FIGS.44A-D present the fluorescent images of the E. coli adsorbed onto theundoped and doped colloidally-templated polymeric surfaces afterstaining with SYTO 9 dye. A control experiment was also performed byincubating the bacterial solution in an unmodified ITO surface.Significant reduction of bacterial adhesion was observed for the undopedsurface (p<0.05) as compared to the control and the doped film. Thisoutcome is consistent with the previous results of Liu et al.⁴⁴ thatbacterial adhesion can be significantly reduced on a superhydrophobicsurface.

Based on the results, the prevention of bacterial cell adhesion on thededoped surface can be explained by the low binding strength between thebacteria and the surface because of the minimized contact between theaqueous media that suspends the bacteria and the surface.²⁴ Nonetheless,the adhesion of more bacteria onto the doped surface is possibly due tothe hydrophilic nature of the surface that favors a better contactbetween the aqueous media and the surface. This result is confirmed whenthe unmodified ITO, which is more hydrophilic and has a relativelysmooth surface than the doped and undoped surfaces, adhered the highestamount of bacteria (FIG. 44D). Moreover, we cannot discount that theincreased bacterial attachment can be related also to the electrostaticinteraction between the net positively-charged polymeric surface,created upon doping and the negatively charged E. coli. ⁴⁵ Although thedetermination of the exact mechanism of the bacterial adhesion is beyondthe scope of this publication, it is possible that the doped surfacewould have some antimicrobial properties, with possible mechanismssimilar to cationic peptides.⁴⁶

Conclusions Section III

Prevention of protein and bacterial adhesion was demonstrated on ananti-wetting and self-cleaning superhydrophobic polythiophene filmfabricated using a combined particle-layering by LB-like method andCV-electropolymerization technique. The fabricated colloidally-templatedpolymeric surface has proven to be highly stable and non-wetting over awide pH range (pH 1-13), temperatures (between 4° C. and 80° C.) andeven when the surface was frozen at −10° C. for more than 4 days.Furthermore, the superhydrophobic surface has demonstrated self-cleaningat a sliding angle of about 3°. By simply manipulating the redoxproperty of the conducting polymer using an external stimuli (e.g.applying a constant potential), the wettability of the surface waseasily changed, which affected the adhesion of fibrinogen and E. coli.Since the switching of the surface wettability can be easily achieved bysimply changing the redox property of the conducting polymer, theproposed methodology maybe useful for fabricating smart coatings ontovarious conducting surfaces, which can be tuned to resist or adsorbprotein and bacterial cell. Current effort is underway for testing thesuperhydrophobic surface on other proteins and bacterial cells andtowards understanding the various mechanism of their adhesion andresistance.

Experiments of Section III Materials and Reagents

Polystyrene (PS) latex microbeads (0.5 μm in diameter, 2.5 wt % solidsin aqueous suspension) were purchased from Polysciences, Inc. and wereused without further purification. Acetonitrile (ACN), sodium n-dodecylsulfate (SDS), and tetrabutylammonium hexafluorophosphate (TBAH),fibrinogen protein, phosphate buffer saline (PBS) tablet were obtainedfrom Sigma-Aldrich. The glass slides (BK 7) for gold (Au) depositionswere acquired from VWR. The tin-doped indium oxide, ITO(In₂[Sn_(x)]O_(3-y), one side coated on glass, sheet resistance ≦30Ωcm⁻²) used for the preparation of superhydrophobic surface waspurchased from SPI Supplies/Structure Probe, Inc. Prior to use, the ITOsubstrate was sonicated in Alconox detergent followed by rinsing withultra pure water. The ITO was then sonicated for 10 min in isopropanol,hexane, and then toluene, respectively, prior to oxygen plasma cleaningfor ˜120 sec. The Au substrate also used for the fabrication ofsuperhydrophobic surface was prepared by thermally evaporating gold of99.99% purity (50 to 100 nm thick) under high vacuum (10⁻⁶ bar) onto theBK 7 glass slide with chromium adhesion layer (˜10 nm thick). The Cr andAu depositions were done at a rate of ˜0.4 Åsec⁻¹ and ˜1.1 Åsec⁻¹,respectively, using a thermal evaporator (Edwards). Prior to use, theAu-coated slide was also cleaned in the oxygen plasma cleaner for 120sec. The deionized water or ultra pure water (resistivity ˜18.2 MΩ·cm)used for the dilution of PS particles was purified by a Milli-QAcademic® system (Millipore Cooperation) with a 0.22 micron Millistackfilter at the outlet. Fibrinogen solution was prepared in PBS solutionat 1 mg/ml concentration. The PBS buffer solution (0.1 M concentration,pH 7.4) was prepared by dissolving 1 tablet of the PBS into 200 ml ofMilli-Q water. The monomer used in the electrochemical polymerizationwas synthesized in our laboratory.

Scheme III.1 Synthesis Route of the Functional and Cross-linking Monomerethyl 2-(2,5-di(thiophen-2-yl)thiophen-3-yl)acetate (G0-3TCOOR)Synthesis of the monomer (G0-3TCOOR), where R═CH₂CH₃)

The synthesis of G0-3TCOOR was carried out by first synthesizing ethyl2-(2,5-dibromothiophen-3-yl)acetate as reported in the literature.³⁵ ¹HNMR (CDCl₃): 6.94 (s, 1H), 4.17 (q, 2H, J=7.15 Hz), 3.55 (s, 2H), 1.27(t, 4H, J=7.14 Hz) as shown in FIG. 45A.

The procedure described by Taranekar et al³⁵ was used to synthesizeG0-3TCOOR. Briefly, ethyl 2-(2,5-dibromothiophen-3-yl)acetate (6.4 g, 10mmol) and 2-(tributylstannyl) thiophene (15 g, 20 mmol) were added to a30 mL dry DMF solution of dichlorobis (triphenylphosphine) palladium(1.3 g, 1.5 mmol). After three freeze-thaw cycles, the mixture washeated at 100° C. for 48 hr. The mixture was cooled to room temperatureand poured into a beaker containing 150 mL of water and subsequentlyextracted with CH₂Cl₂. The extracted CH₂Cl₂ mixture was dried withNa₂SO₄. After filtering and evaporating the solvent, the crude productwas purified by chromatography on silica gel using toluene as an eluent.The final product was obtained in 85% yield as pale yellow oil. ¹H NMR(CDCl₃): δ 6.8-7.2 (m, 7H), 4.19 (q, 2H, J=7.15 Hz), 3.72 (s, 2H), 1.27(t, 4H, J=7.14 Hz) as shown in FIG. 45B.

PS Particle Layering

The layering of PS microbeads (or formation of colloidal crystals) wasaccomplished using a similar procedure described by Grady andco-workers. The method is called Langmuir-Blodgett (LB)-like technique.It allows the formation of a monolayer of PS particles onto flatsurfaces without using the conventional LB set-up, which employsfloating barriers. Briefly, the LB-like technique involved the verticallifting of the substrate at a controlled rate from a solution withdispersed colloidal particles. As shown in FIG. 32A, the substrate wasattached into the dipper motor via Teflon clip and was dipped into anaqueous solution of PS particles (1 wt. %) and SDS (34.7 mM) asspreading agent. Note that much higher concentration than 34.7 mM of theSDS will result in multiple layers of highly disordered latex sphereswhile a low concentration will not form full area coverage in hexagonalarray. Then the substrate was withdrawn vertically from the solution ata lift-up rate between 0.1 to 0.3 mm/min. Finally, the substrate was airdried for a few minutes.

The addition of anionic surfactant (SDS) has been explained to increasethe ionic strength of the solution, and thus creating a driving forcefor the migration of particles from the bulk solution to the air-liquidinterface.²⁷ Also, the surfactant molecules at the air-liquid interfacehas been reported to slow down the evaporation rate of thelatex-surfactant solution with respect to the latex solution alone,giving more time for the particles to rearrange and form highly orderedarrays on the substrate as the liquid film evaporates.²⁷ The other rolesof the surfactant towards the formation of well-ordered arrays of latexspheres have been elaborated elsewhere.

Preparation of Superhydrophobic Surface

The superhydrophobic conducting surface was fabricated by simpletwo-step process such as (1) layering of PS latex microbeads ontoconducting substrates like Au and ITO slides, and (2)electropolymerization of the monomer into the PS-coated slides. Thelayering of PS latex beads was prepared using a similar proceduredescribed earlier by Grady and co-workers.²⁷ The substrate was attachedvertically into the dipper motor via a Teflon clip and was dipped into asolution of PS particles (1 wt % in Milli-Q water) and SDS (34.7 mM) asspreading agent. The substrate was then withdrawn vertically from thesolution at a lift-up rate of 0.1-0.3 mm/s. The substrate was then driedby suspending it in air for a few min. After the layering of the latexspheres, the monomer (5 mM G0-3TCOOR in ACN with 0.1 M TBAH assupporting electrolyte) was electropolymerized onto the PS-coatedsubstrate (Au or ITO) as the working electrode in a standard threeelectrode measuring cell with platinum (Pt) wire as the counterelectrode and Ag/AgCl wire as the reference electrode. Theelectropolymerization was done using cyclic voltammetric technique in afabricated electrochemical cell (Teflon made). The potential was scannedbetween 0 V to 1.1 V (and also 0V to 1.5 V) for 15 cycles at a scan rateof 5 mV/s. Note that the use of very low scan rate will result to theformation of thicker polymer coatings. Also, it is possible to do thisdeposition of polymer film by chronoamperometric or potentiostaticmethods. After electrodeposition, the film was thoroughly washed in ACN(at least 3 times) to remove the excess monomer and physically adsorbedpolymer or oligomer, and a post-polymerization monomer-free scan (in asolution of ACN with 0.1 M TBAH) was performed by using exactly the sameelectrochemistry set-up and settings but for 1 CV cycle only. Finally,the electropolymerized film was thoroughly dried in vacuum for at least1 hr prior to any characterizations. To dope (or undoped) the polymericsurface, a constant oxidation potential of 1.05 V (or 0 V) was appliedfor 30 minutes onto the polymeric surface (working electrode), which wasimmersed in ACN with 0.1 M TBAH along with the reference (Ag/AgCl) andcounter (Pt wire) electrodes.

Characterizations

Cyclic voltammetry (CV) was performed in a fabricated electrochemicalcell (Teflon-made, with a diameter of 1.0 cm and volume of 0.785 cm³)using a conventional three-electrode cell using an Autolab PGSTAT 12potentiostat (Brinkmann Instruments now Metrohm USA, Inc.). Thepotentiostat is controlled by GPES software (version 4.9).

Profilometry of model Alpha-Step 200 was used to measure the thicknessof the polymeric surface. The Alpha-Step 200 profilometer can accuratelymeasure the surface profiles below 200 Å and up to 200 μm. A low stylusforce of 5 mg was used during the scanning to avoid damaging the polymersurface. The measurements were done at least 10 times on different areasof the sample surface under ambient and dry conditions.

The static contact angle measurements were done using a CAM 200 opticalcontact angle meter (KSV Instruments Ltd) with CAM 200 software. Theexperiment was carried out by slowly moving upward the sample stage withthe sample surface on top to come close onto the water droplet (˜1 μL)that was suspended at the tip of the micro syringe (200 μL). The readingof the contact angle was done after 30 seconds when the droplet has beenmade into the surface. The measurements were performed for at least fivetrials at different areas of the sample surface and were replicated inthree more samples. Note that the WCA value was acquired only when thewater droplet was dropped at a relatively far distance (ca 0.3 cm) awayfrom the surface since no reading can be measured if the droplet is tocome into contact with the substrate. For dynamic contact anglemeasurements, the angles were measured using a Ramé-Hart model 100contact angle goniometer. The liquids were dispensed and withdrawn usinga Matrix Technologies micro-Electrapette 25. Contact angles werecollected and averaged from measurements on four distinct slides usingthree separate drops per slide.

Atomic force microscopy (AFM) analysis was carried out in a piezoscanner from Agilent Technologies. The scanning rate was between 0.8-1.5lines/s. Commercially available tapping mode tips (TAP300, Silicon AFMProbes, Ted Pella, Inc.) were used on cantilevers with a resonancefrequency in the range of 290-410 kHz. The scanning of the PS-coated Auand ITO was performed under ambient and dry conditions. All AFMtopographic images (AAC tapping mode) were filtered and analyzed byusing Gwyddion software (version 2.19). Only the PS-coated substrateswere scanned in the AFM. Because of the formation of very roughsurfaces, the electropolymerized films on PS-coated substrates were onlyscanned in the SEM.

The attenuated total reflection infrared (ATR FTIR) spectra wereobtained on a Digilab FTS 7000 equipped with a HgCdTe detector from 4000to 600 (cm⁻¹) wavenumbers. All spectra were taken with a nominalspectral resolution of 4 cm⁻¹ in absorbance mode. All films weremeasured under ambient and dry conditions for several trials atdifferent areas of the sample surface.

The morphology of the samples was examined by field emission scanningelectron microscopy (FE-SEM) using a JSM 6330F JEOL instrument operatingat 15 kV. Prior to SEM analysis, the films were thoroughly dried undervacuum for at least 24 hrs.

Quartz crystal microbalance (QCM) measurement was used for theadsorption of fibrinogen. The QCM apparatus, probe, and crystals weremade available from Maxtek Inc. (Inficon). The AT-cut polished QCMcrystals (5 MHz) was used as the working electrode. The data acquisitionwas done with an R-QCM system equipped with a built-in phase lockoscillator and the R-QCM Data-Log software. The QCM crystals were alsocleaned (˜120 sec) with an oxygen plasma etcher (Plasmod, March)immediately prior to use. The measurement was done by allowing a stablebaseline in air prior to the injection of the protein solution. The QCMcrystal with the polymeric surface was incubated in the fibrinogensolution (1 ml volume) for ˜950 minutes. Afterwards, the proteinsolution was removed using micro pipette, and the crystal was rinsedwith Milli-Q water to eliminate/minimize the salts from the PBS buffer.Then a stable baseline in air was again achieved after drying in the N₂gas.

Bacterial Adhesion Measurements

Bacterial Culture

A single isolated Escherichia coli K12 MG1655 (E. coli) colony wasinoculated in 5 mL Tryptic Soy Broth (TSB) overnight at 35° C. Thebacterial culture was centrifuged at 3000 rpm for 10 minutes, and thebacteria pellet was resuspended in TSB. The optical density of thesuspension was adjusted to 0.5 at 600 nm, which corresponds to aconcentration of 10⁷ colony forming units per milliliters (CFU/ml). Thedoped, undoped colloidal-polymeric films and unmodified ITO substratewere individually placed in a 12 well-plate (Falcon). To each well wasadded 1.0 ml of bacterial culture and then incubated at 37° C. (withoutshaking) for 2 h. The samples were then removed and immediately prior toviewing were stained with 3 ml of SYTO 9 dye solution for 10 minutesfrom Molecular Probes (Leiden, The Netherlands) marking viable bacterialcells. The surfaces were placed in microscope slides, covered with acover slip and imaged using BX 51 Olympus Fluorescent Microscopeequipped with a DP72 digital camera under 100× objective. All imageswere acquired and analyzed using cell Sens Dimension software (Olympus).

Statistical analysis. The amount of attached bacterial cells wasexpressed as the mean number of bacteria±standard deviation of fourexperiments (3 replicates prepared at 2 different times). Statisticaldifferences between median values were done using pair-wise comparisonby ANOVA on ranks test using Sigma Plot Software (version 11).Significance was accepted at a level of p<0.05.

REFERENCES OF SECTION III

The following references were cited in this section.

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Detailed Description of Section IV Patterned Surfaces Combining PolymerBrushes and Conducting Polymer Via Colloidal TemplateElectropolymerization Introduction Section IV

Recently, there has been a significant interest in the fabrication ofpatterned polymer surfaces because of potential applications insurface-based technologies such as microfluidic devices,chemical/biosensors, platforms for tissue engineering, etc.¹ To date,polymer brushes are widely used in patterning surfaces due to theirrobustness, broad range of chemical and mechanical properties, andability to modify surface properties,² and thus an ideal surrogate forself-assembled monolayers (SAM)s. Despite the numerous applications ofpatterned polymer surfaces, there have been a limited number ofstrategies reported toward the formation of laterally well-definedbinary composition patterned brushes.³ Most of the methods used involveexpensive, tedious and complex lithographic techniques,⁴ which limitstheir practical applications.

Another material of high interest are conducting polymers, which are aversatile class of organic materials with electrical, optical, andelectrochemical properties that are easily modified by design andsynthesis. They are useful as display materials, semi-conductors,electrochromic devices, fluorescent materials, non-linear opticalmaterials, electromagnetic shielding, and various types of industrialcoatings for anti-corrosion and anti-static purposes.⁵ Due to theirunique properties, conducting polymers⁶ are also being exploited inmaking 2D nano/microstructured arrays because of the many applicationssuch as photonic crystals, diffraction gratings, biosensors, andsurface-enhanced Raman scattering (SERS).⁷

The electropolymerization technique endows several advantages—ease incontrol of thickness and lateral dimension of the pattern, site-directedpatterning, and deposition over large surface areas onto variousconducting substrates. One unique electrodeposition approach is bytemplate-assisted electropolymerization, which has remained largelyunexplored for 2-D patterning. To our knowledge, this is the firstreport on binary composition patterned surfaces combining a conductingpolymer and a polymer brush via a simple approach of colloidaltemplate-assisted electropolymerization followed by growing the polymerbrush, using surface initiated atom transfer radical polymerization(SI-ATRP). The present invention is also the first account on dualpatterned inverse colloidal crystals (in a single layer assembly) ofelectrodeposited conducting polymer and an SI-ATRP initiator.

Summary of Inventions Section IV

Embodiments of the generic method of this invention should be useful formaking different types of binary patterned surfaces using differentcombinations of polymer brushes, conducting polymers, and self-assembledmonolayers. The importance of such combinations may be found inredox-active (t-conjugated polymer-based) stimuli-responsive polymerbrushes and modulation of electro-optical properties simultaneous withchanges in solvent swelling properties (polymer brushes), dependent onthe binary composition and mode or size of patterning.

Detailed Description Section IV

The protocol for stepwise patterning of binary patterned polymersurfaces is illustrated in FIG. 46A to FIG. 47A. First, the layering ofpolystyrene (PS) microspheres particles was done on flat conductingsubstrates such as indium tin oxide (ITO) and gold (Au) using theso-called Langmuir-Blodgett (LB)-like technique,⁸ which uses only avertical lifting motor (FIG. 46A, step 1). The LB-like technique allowsthe monolayer deposition of particles in hexagonal arrangement on thesubstrate (FIGS. 46B and 46C), which serves as a template for theelectrodeposition of conducting polymer. The monolayer ordering of themicrosphere particles (called colloidal crystals) has been previouslyreported to be dependent on the vertical drawing speed of the LB-liketechnique, and the concentration of the particles and surfactant (sodiumn-dodecyl sulfate or SDS) in solution.⁸ The high ordering of theparticles on the surface is well-preserved (FIGS. 46D and 46E) evenafter the electropolymerization of the conducting polymer(polycarbazole) via cyclic voltammetry (CV). Note that this result isonly made possible by using the right solvent like acetonitrile duringelectropolymerization. Other solvents such as water, dichloromethane(DCM), toluene, and tetrahydrofuran (THF) tend to wash the particles anddestroy the ordering. The electrodeposition of the conducting polymer isobserved by the increasing reduction-oxidation (redox) peak (between 0.7to 0.9 V) of the poly(carbazole) as the potential is sweep from 0V 1.1 Vfrom cycle 1 to 20 (FIG. 48). Moreover, the decrease in frequency (ΔF)of the quartz crystal microbalance (QCM) accompanying the increase ofthe redox peak (in-situ electrochemistry-QCM measurements) corroboratesthe electrodeposition of the conducting polymer onto the PS Au coatedsubstrate (FIG. 49). Using the Sauerbrey equation, an average of 8.97 μg(dry mass) is adsorbed onto the QCM crystal due to the electrodepositionof the polymer film. The advantage of using the CV forelectropolymerization is the ability to control the deposition of apolymer and the two dimensional size of arrays by variouselectrochemical process variables and the size of the colloidal spheres.For instance, the conducting polymer is electrodeposited only at theinterstitial void spaces underneath and in-between the PS particles,which is substantiated after removing the PS particles on the surface bywashing with THF (2×, 30 min). The removal of the PS particles thatserve as sacrificial templates for electropolymerization creates amonolayer array of conducting polymer network (called inverse colloidalcrystals) of poly(carbazole) with pre-grafted ethylene glycol (EG) units(poly(CBzTEGG1) (FIGS. 46F and 46G). Previously, surfaces modified withEGs have been known to resist the non-specific adsorption of proteins,and thus may find potential applications as biomedical coatings.⁹ TheSEM analysis confirms the AFM topography measurements of the inversecolloidal crystals, which depicts a high periodicity of the 500 nm PSimprinted film (FIG. 46H). The size of the cavity matches the size ofthe PS particle template (˜500 nm) as determined by the SEMcross-sectional analysis (FIG. 46H right). The AFM line profiledetermines an average height of the cavity equivalent to 29.05±0.60 mm.The exact elemental analysis (C, N, O) as shown in Table IV.1 on thesurface by complimentary x-ray photoelectron spectroscopy (XPS) confirmsthe electrodeposition of poly(carbazole) as shown in FIG. 50.

TABLE IV.1 Summary of Atomic Concentrations Determined from XPS C N OSubstrate (%) (%) (%) CBzTEGG1 Theoretical value 78.33 3.88 17.77CBzTEGG1 onto Experimental 78.53 4.03 17.45 500 nm PS/Au (after PSremoval)

Moreover, the UV-Vis spectrum as shown in FIG. 51 of the surface revealsthe signature peaks of a typical poly(carbazole) electrodeposited filmon ITO with peaks centered at ˜450 nm and ˜890 nm, which are consistentwith our earlier results.¹⁰ These peaks are assigned to the π-π*transistion of the poly(carbazole)¹¹ and the polaronic band formation ofthe conjugated poly(carbazole) species and their complex redox ioncouple with hexafluorophosphate ions,^(10,12) respectively.

To create a highly ordered and dual pattern surface as shown in FIG.47A, the inside cavities of inverse colloidal crystals of conductingpolymer network were first back-filled with a silane molecule,11-(2-Bromo-2-methyl)propionyloxy) undecyltrichlorosilane or Si—Br(details of the synthesis are described herein), which is an ATRPinitiator used for grafting polymer brushes. The adsorption of the Si—Brself-assembled monolayer (SAM) into the inner holes is clearly seen inthe AFM topography images as shown in FIGS. 47B and 47C, which is alsoevident in the decrease of the peak-to-baseline height in the AFM lineprofile analysis as shown in FIG. 47D. This dual pattern surface isamplified upon grafting the polymer brush atop the initiator layer. Thedifference in height before and after Si—Br SAM immobilization (˜1.8 nm)into the cavities is equivalent to the theoretical length of themolecule calculated using Spartan, Wavefunction quantum calculations(FIG. 52). Also, the root-mean-square (rms) roughness value of the innerholes has increased to 3.15±0.36 nm from 2.45±0.32 nm after the backfilling step. Note that the rms value of bare ITO is equivalent to2.00±0.19 nm. The adsorption of the Si—Br SAM onto the macroporouspolymer array is also confirmed by the increasing hydrophobicity of thesurface. Its water contact angle (WCA) had increased to 90°±2° from83°±1° (WCA of inverse opals on ITO). Then thepoly(n-isopropylacrylamide) (pNIPAM) brush was grown (˜15 minutesreaction time) from the inner cavities via the ATRP initiator underlyingsurface. Similarly, the growth of the pNIPAM brush is shown in the AFMtopography images as shown in FIGS. 47E and 47F. Now the back filling ofthe holes is more apparent with the growth of the polymer brush. Theline profile analysis as shown in FIG. 47G validates the results asshown by the decrease of the peak-to-baseline height, which is lowerthan the Si—Br SAM. An average increase of ˜12 nm in height of theinside layer is determined from the line profile. Moreover, the rmsvalue of the inside cavities has increased to 4.71±0.82 nm, which isclose to the rms value (4.52±0.56 nm) of the pNIPAM brush grown onunpatterned surface (bare ITO).

To further verify the adsorption of the initiator and pNIPAM brush, XPSwas used to analyze the patterned surface. The presence of the bromine(Br 3d) peak¹³ as shown in FIG. 53A in the XPS high resolution scan,which is a unique elemental marker due only to the ATRP initiator,confirmed the immobilization of Si—Br. Likewise, the growth of thepNIPAM brush is evidenced by the increased in signal of the elements (C,N, O) in the survey scan as shown in FIG. 53B, which is more obviouswith the N 1s peak (˜400 eV).^(13, 14a) Also, the survey scan revealsthat the pattern surface is clean since the elements present are dueonly to the conducting polymer and the polymer brush. The bromineelement as shown in FIG. 53B (inset), which is also a distinctiveelement of the pNIPAM brush,^(13, 14a) is better seen in the highresolution scan. A more compeling evidence about the growth of thepolymer brush is given by the attenuated total reflectance infrared (ATRIR) analysis as shown in FIG. 53C, which shows the characteristic peaksof pNIPAM as shown in FIG. 53C (green curve) reported in literature:¹⁴amide I band (1640 cm⁻¹) due to primary amide —C═O stretching, amideband II (1540 cm⁻¹) due to secondary amide -N-H stretching, secondaryamide —N—H stretching (3300-3500 cm⁻¹), and —CH₃ and —CH₂ asymmetricstretching (2800-3000 cm⁻¹). The same peaks are confirmed with thespectrum of the pNIPAM brush as shown in FIG. 53C (blue curve) grown onunpattern surface (bare ITO). As expected, the peak intensities in thespectrum of the pNIPAM brush grafted on bare ITO is higher than thepNIPAM pattern surface, which is attributed to the thicker brushformation in the unpatterned surface (ellipsometry thickness˜17.82±3.77nm). Note that the ATR IR measurements is less sensitive to the analysisof thinner films. The macroporous conducting polymer network (inversecolloidal crystals) was also scanned in the ATR IR. The spectrum asshown in FIG. 53C (black curve) divulges the signature peaks of thepolycarbazole¹⁵ with anchored ethylene glycol units: —C═O stretching(1720 cm⁻¹) due to the pre-grafted carboxylic acid moiety, broad —OHstretching (3050-3550 cm⁻¹) due to the hydroxy terminated EG unit, —C═Cstretching (1593 cm⁻¹) due to the carbazole head group, and —CH₂ and —CHasymmetric stretching (2800-3000 cm⁻¹). Noteworthy, the emergence of the—N—H stretch (3300-3500 cm⁻¹) due to pNIPAM brush (shifting of theoriginal —OH stretch) and still appearance of the —C═O stretch(noticeable shoulder peak, FIG. 53C (inset)) due only to poly(carbazole)with EG moiety proves the formation of a dual pattern surface as shownin FIG. 53C (green curve), which is earlier observed in the AFMtopography measurements. Finally, the current sensing (CS)-AFM incontact mode was used to analyze the dual pattern surface. Unlike thetapping mode AFM, the topography image determined from the contact modehas lesser resolution but still the pattern is evident as shown in FIG.54A. Nevertheless, the macroporous polymer network is better seen in thefriction image as shown in FIG. 54B and current image as shown in FIG.54C based on color distribution, which presents a good image contrastdue to the difference in conductivity of the two materials with a highconductance corresponding to the honeycomb web-like array of conductingpolymer. This finding is coherent with the previous current image of anordered honeycomb of 4-dodecylbenzesulfonic acid (DBSA)-dopedpolyaniline (PANI).¹⁶ Another coercing evidence is the outcome of theconductivity measurements by CS-AFM. For instance, the wall cavity ofthe pattern (AFM tip positioned at area 1, FIG. 54D) that is mainlypoly(CBzTEGG1) exhibits a typical junction, I-V curve as shown in FIG.54E of a conducting polymer¹⁷ which is consistent with our earlierreport.^(17a) In contrast, the inside region of the cavity (AFM tippositioned at area 2, FIG. 54D) shows a nil current depicted by a flatline in the I-V curve (FIG. 54F). This result is expected since thisarea is composed of the pNIPAM brush that is non-conducting.Furthermore, the observed I-V (FIG. 54E) curve on the wall cavity isasymmetric with respect to 0 V, suggesting an archetypalsemi-conductor-metal junction.^(17a) Therefore, the CS-AFM is a powerfultechnique to verify the formation of patterned surfaces especially inthe case of differing conductivity of the materials. Note that absoluteconductivity values cannot be determined from this type of measurements(non-ohmic) but rather the technique is used mainly to differentiate thearea of the conducting polymer (even at dedoped state) from the polymerbrush.

In conclusion, we have developed a facile and new approach to creatingtopologically and chemically defined polymer surfaces by combining thetechniques of colloidal sphere layering, electropolymerization andpolymer brush synthesis. In principle, with the versatility of themethod, it should be obvious to make dual or binary compositionpatterned surfaces using different polymer brushes, conducting polymers,self-assembled monolayers or a combination of any two. The fabricatedbinary patterned surface finds potential application in developing adual responsive sensor film with specific composition of redox activeand electrically conducting polymers within a periodic vicinity ofsurface attached molecular and macromolecular moieties for tetheringspecific receptors. The presence of the conducting polymerinterconnected network can be used to control the stimuli-response in ahydrogel polymer brush link pNIPAM or enable control of p-conjugatedpolymer electro-optical properties combined with solvent-effects by thepolymer brush.

Experiments of Section IV Materials

The polystyrene (PS) latex microbeads (500 nm size, 2.5 wt. % solids inaqueous suspension) were purchased from Polysciences, Inc. and were usedwithout further purification. The acetonitrile (ACN), sodium n-dodecylsulfate (SDS), tetrahydrofuran (THF), methanol (MeOH),tetrabutylammonium hexafluorophosphate (TBAH), n-Isopropylacrylamide(NIPAM),N,N,N′,N′,N″-pentamethyldiethylenetriamine (PMDETA), and copper(I) bromide (CuBr) were obtained from Sigma-Aldrich. The monomer(CBzTEGG1) used in the electropolymerization was synthesized asdescribed below. The PS solution used for layering contains 1 wt. % PSparticles and 34.7 mM SDS (spreading agent) in Milli-Q water.

CV was performed in a fabricated electrochemical cell (Teflon-made, witha diameter of 1.0 cm and volume of 0.785 cm³) using a conventionalthree-electrode cell using an Autolab PGSTAT 12 potentiostat (MetroOhm,Inc). AFM measurements were done on a PicoScan 2500 AFM from AgilentTechnologies using tapping mode with scanning rate between 1-1.5lines/s. Commercially available tapping mode tips (TAP300-10, siliconAFM probes, Tap 300, Ted Pella, Inc) were used on cantilevers with aresonant frequency in the range of 290-410 kHz. All AFM topographicimages were filtered and analyzed using the Gwyddion software (version2.19). The CS-AFM analyses in contact mode were done on the same set upusing Pt-coated Si₃N₄ tip with radius around 20 nm and force constant of0.5 N/m. Ellipsometry was used to measure the thickness of the polymerbrush film on Au substrate using the Multiskop ellipsometer (OptrelGmbH, Germany) equipped with a 632.8 nm laser (at 60° angle ofincidence). The measured values of delta and psi were used to calculatethe thickness of the film using an integrated specialized software(Elli, Optrel) that was provided with the instrument. The thickness ofthe pNIPAM brush was calculated using a multilayer flat film model withan assumed refractive index of 1.5.^(14a,18) Contact angle measurementswere accomplished on a CAM 200 optical contact angle meter (KSVInstruments Ltd). XPS measurement (at take off angle of 45° from thesurface) were carried out on a PHI 5700 X-ray photoelectron spectrometerwith a monochromatic Al Kα X-ray source (hn=1486.7 eV) incident at 90°relative to the axis of a hemispherical energy analyzer. The ATR FTIRspectra of the film on ITO substrate were obtained on a Digilab FTS 7000equipped with a HgCdTe detector from 4000 to 600 (cm⁻¹) wavenumbers witha nominal spectral resolution of 4 cm⁻¹ in absorbance mode. SEM analysiswas done in field emission scanning electron microscopy (FE-SEM) using aJSM 6330F JEOL instrument operating at 15 kV.

Preparation of Patterned Surfaces

First, the formation of colloidal crystals using PS on ITO and Au wasaccomplished by following the procedures reported by Grady andco-workers.⁸ This step was followed by CV-electropolymerization (50mV/s, 0V-1.1V, 20 cycles) of the monomer (5 mM CBzTEGG1 in ACN with 0.1M TBAH as supporting electrolyte). Then the PS microspheres were removedfrom the surface by dipping the substrate into THF (for 30 min, twice)to create an inverse colloidal crystals. To prepare a dual patternedsurface, the pre-patterned (inverse opal) substrate was placed into asolution of 8 mM ATRP initiator anhydrous toluene (for 19 hr withoutstirring, 60° C.). The initiator-backfilled pre-patterned substrate wasthoroughly rinsed sequentially with toluene, followed by drying withnitrogen gas. Note that 11-(2-Bromo-2-methyl)propionyloxy)undecyltrichlorosilane was used as initiator for patterned surface onITO substrate while 11-mercaptoundecyl 2-bromo-2-methylpropanoate forpatterned surface on Au substrate. To grow the brush, the initiatorback-filled inverse opal substrate was placed into a schlenk tube anddegassed with nitrogen. During this time a 0.16 M solution of NIPAM witha 1:1 ratio of methanol/water and 28 μL PMDETA was subjected to 3 cyclesof freeze pump thaw technique. A third schlenk tube contained CuBr (6.35mg, 0.04 mmol) was also degassed with nitrogen. Once the freeze pumpthaw cycles were completed the solution containing the NIPAM, MeOH/H₂O,and PMDETA were transferred into the schlenk tube containing the CuBrusing a syringe. After 5 min of stirring, this solution was thentransferred into the schlenk tube containing the substrate with theATRP-initiator selectively bound to the inner cavity of the polymernetwork array. After the desired time (15 min), the substrate wererinsed with water, methanol and placed into a vial with a 1:1 MeOH/H₂Oratio solution over night to remove any unbound NIPAM, ligand, or metalcatalyst.

References for the Detailed Description of Section IV

The following references were cited in this section.

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Synthesis of the Functional and Cross-linking Monomer (CBzTEGG1)¹Synthesis of 9-(4-bromobutyl)-9H-carbazole [CBz Br]

The synthesis of CBz Br was done by combining carbazole (20.64 g, 0.1236mol), 1,4-dibromobutane (132 mL, 1.095 mol), tetrabutylammonium bromide(4 g, 0.0124 mol), toluene (200 mL), and 50% NaOH (200 mL) The resultingmixture was stirred at 45° C. for 3 hrs and continuously stirred at roomtemperature overnight. The clear, yellow organic layer was then washedwith 100-mL portions H₂O followed by 100 mL brine solution. This wasthen dried over anhydrous Na₂SO₄. The solvent was removed via rotaryevaporator and the excess 1,4-dibromobutane via vacuum distillation.After which, the resulting cream-like solid residue was slowly dissolvedin small portions of CH₂Cl₂. The yellow-brown solution wasrecrystallized using ethanol. The resulting white solid residue wasdried under vacuum overnight. ¹H NMR (6 ppm in CDCl₃): 8.12 (d, 2H),7.22-7.48 (m, 6H), 4.36 (t, 2H), 3.38 (t, 2H), 1.95-2.07 (m, 4H).

Synthesis of methyl 3,5-bis(4-(9H-carbazol-9-yl)butoxy)benzoate[CBzCOOCH₃G1]

The synthesis of compound CBzCOOCH₃G1 was done by combining CBz Br(27.93 g, 0.0923 mol), methyl-3,5-dihydroxybenzoate (6.49 g, 0.0386mol), and 18-crown-6 (2.416 g) in acetone. To the resulting yellowsolution mixture was added K₂CO₃ (29.46 g) and this was left at refluxfor 3 days. This was continuously stirred for 2 days. The solvent wasthen removed using a rotary evaporator. Water was added to the creamsolid residue and the desired compound extracted with dichloromethane.The organic layer was subjected to rotary evaporation until 20-25 mL wasleft just to dissolve the solid residue. To this was added ethyl acetateto precipitate out the desired white solid compound. ¹H NMR (6 ppm inCDCl₃): ¹H NMR (6 ppm in CDCl₃): 8.20 (d, 4H), 7.49-7.12 (m, 16H), 6.54(s, 1H), 4.40 (t, 4H), 3.95 (t, 4H), 3.88 (s, 3H) 2.11-2.04 (m, 4H),1.87-1.82 (m, 4H).

Synthesis of 3,5-bis(4-(9H-carbazol-9-yl)butoxy)benzoic acid [CBzCOOHG1]

CBzCOOCH₃G1 (2 g, mol) was dissolved in THF. Ethanol (50 mL) was thenadded to the solution. To this was added KOH (10 eq). This was thenrefluxed for 2 days. After which, the reaction mixture was cooled downand acidified to pH=2-3. This was then extracted with dichloromethaneand the solution washed with NaHCO₃. After drying with Na₂SO₄, thedesired product was precipitated in hexane. ¹H NMR (6 ppm in CDCl₃): ¹HNMR (d ppm in CDCl₃): 8.09 (6, 4H, J=7.8), 7.46-7.14 (m, 14H), 6.55 (s,1H), 4.39 (t, 4H, J=6.7), 3.93 (t, 4H, J=6.0), 2.08-2.03 (m, 4H),1.84-1.82 (m, 4H).

Synthesis of2-(2-(2-(2-hydroxy)ethoxy)ethoxy)ethyl-3(4-(9H-carbazol-9-yl)butoxy)-5-(4-(9H-carbazol-9-yl)butoxy))benzoate[CBzTEGG1]

In a one-necked flask were combined CBzCOOHG1 (100 mg, 0.1676 mmol),tetraehylene glycol (97.53 mg, 0.5027 mmol), and 4-dimethylaminopyridine(2.909 mg, 0.0238 mmol). The mixture was dissolved in minimal amount ofdichloromethane, bubbled with nitrogen, and placed in an ice bath. Afterwhich, a solution of dicyclohexylcarbodiimide (47.94 mg, 0.2327 mmol) indichloromethane was added dropwise to the reaction mixture. This wasthen stirred vigorously for 30 mins, warmed to room temperature andstirred for 2 days. The solid by-product was filtered off and thefiltrate was washed with water (5×) and brine solution (2×). The mixturewas then subjected to column chromatography using 3% MeOH/CH₂Cl₂. Thedesired product was further purified by precipitating out otherby-products with ethyl acetate. The supernatant was then concentratedand dried under vacuum. ¹H NMR (6 ppm in CDCl₃): 8.19 (6, 4H, J=7.8),7.56-7.49 (m, 8H), 7.35-7.29 (m, 4H), 7.24 (d, 2H, J=2.4), 6.63 (t, 1H,J=2.7), 4.55 (t, 2H, J=4.8), 4.48 (t, 4H, J=6.6), 4.03 (t, 4H, J=6.0),3.89 (t, 2H, J=4.8), 3.78-3.61 (m, 12H), 2.22-2.12 (m, 4H), 1.97-1.88(m, 4H). MALDI-TOF-MS for CH₄₇H₅₂O₈N₂, m/z: calcd, 772.9364 [M+]. found,772.7447.

Synthesis of 10-Undecen-1-yl 2-Bromo-2-methylpropionate

A similar synthetic scheme was conducted as followed.^(x) To a solutionof 4.257 g (25 mmol) of ω-undecylenyl alcohol in 25 mL of drytetrahydrofuran was added 2.1 mL of pyridine (26.5 mmol) by dropwiseaddition of 3.10 mL of 2-bromoisobutyryl bromide (25 mmol). The mixturewas stirred at ambient temperature for 8 hours. The remaining THF wasremoved under reduced pressure followed by dilution with hexane (50 mL)The mixture was washed with 2 M HCl solution and twice with water (50ml). The organic phase was dried over sodium sulfate and filtered. Thesolvent was removed from the filtrate under reduced pressure yielding acolorless oil (89%). ¹H NMR (500 MHz, CDCl₃) δ: 1.22-1.45 (br m, 12H);1.62-1.75 (m, 2H); 1.94 (s 6H); 2.05 (q, 2H, J) 6 Hz); 4.17 (t, 2H, J=9Hz); 4.9-5.05 (m, 2H); 5.72-5.9 (m, 1H) ppm.

Synthesis of 11-(2-Bromo-2-methyl)propionyloxy)undecyltrichlorosilane²

To a dry flask 1.35 g (4.23 mmol) of 10-undecen-1-yl2-bromo-2-methylpropionate and 4.2 mL of trichlorosilane (42.6 mmol)were added. This was followed by the addition of Karstedt catalyst (4μL, 100 ppm Pt equivalents). The reaction was allowed to stir for 6 h.The solution was immediately filtered through a plug of silica gel toremove the “Pt” catalyst. The excess trichlorosilane was removed underreduced pressure. The compound was used as such. Further purificationcan be done via vacuum distillation (80-85° C. at 2.0×10⁻² mmHg). Whennot the compound was not in use, it was stored in the drybox at 5° C. ¹HNMR (500 MHz, CDCl₃) δ: 1.23-1.45 (br m, 16H); 1.54-1.75 (m, 4H); 1.93(s 6H); 4.16 (t, 2H, J=9 Hz) ppm.

Initiator Immobilization³

Pre-patterned ITO slides were placed it into an 8 mM initiator anhydroustoluene solution for 19 h without stirring at 60° C. Theinitiator-modified Si wafer was thoroughly rinsed sequentially withtoluene, followed by drying with nitrogen gas. The initiator-modified Siwafer was either immediately used for surface polymerization or storedin a desiccator under vacuum.

Synthesis of 11-mercaptoundecyl 2-bromo-2-methylpropanoate⁴

The thiol initiator (BrC(CH₃)₂COO(CH2)₁₁SH) was synthesized asreported.^(z) A self-assembled monolayer (SAM) of the thiol initiatorwas obtained by immersing clean, gold-coated Si substrates in a 1 mMethanolic solution of the thiol initiator for 1 day. After incubation,the substrates were washed with copious amounts of ethanol, and thenrinsed again in ethanol to remove unbound thiols. The samples werefinally dried with nitrogen.

Polymerization of NIPAM

The pre-patterned-coated slides with backfilled ATRP initiators placedinto a schlenk tube and degassed with nitrogen. During this time a 0.16M solution of NIPAM with a 1:1 ratio of methanol/water and 28 μL pentamethyl diethyl triamine (PMDETA) was subjected to 3 cycles of freezepump thaw technique. A third schlenk tube contained CuBr (6.35 mg, 0.04mmol) was also degassed with nitrogen. Once the freeze pump thaw cycleswere completed the solution containing the NIPAM, MeOH/H₂O, and PMDETAwere transferred into the schlenk tube containing the CuBr using asyringe. After 5 min of stirring, this solution was then transferredinto the schlenk tube containing the slide with the ATRP-initiator boundto it. After the desired time the slide were rinsed with water, methanoland placed into a vial with a 1:1 MeOH/H₂O ratio solution over night toremove any unbound NIPAM, ligand, or metal catalyst.

Instrumentation Electrochemistry

Cyclic voltammetry were performed in a conventional three-electrode cellusing an Autolab PGSTAT 12 potentiostat (Brinkmann Instruments nowMetroOhm USA). The potentiostat was controlled by GPES software (version4.9). The electropolymerization of the monomer (FIG. 46C) is done usingcyclic voltammetric (CV) technique in a standard three electrodemeasuring cell (fabricated electrochemical cell with a diameter of 1.0cm and 0.785 cm³, Teflon made) with platinum wire as the counterelectrode, Ag/AgCl wire as the reference electrode, and the bare Au orPS coated Au substrate as the working electrode.

Quartz Crystal Microbalance (QCM)

The QCM apparatus, probe, and crystals were made available from Maxtek,Inc. The AT-cut polished Au-coated QCM crystals (5 MHz) with 13 mmdiameter was used as the working electrode. The data acquisition wasdone with an R-QCM system equipped with a built-in phase lock oscillatorand the R-QCM Data-Log software. The resulting change in frequency canthen be used to calculate the mass change due to the adsorbed materialonto the QCM crystal using the Sauerbrey equation:⁵

$\begin{matrix}{{\Delta \; F} = \frac{{- 2}F_{q}^{2}\Delta \; m}{A\sqrt{\rho_{q}\mu_{q}}}} & \left( {{IV}{.1}} \right)\end{matrix}$

where ΔF 1s the change in frequency, m is the mass change, F_(q) (=5MHz) is the resonant frequency of the QCM crystal, A (=1.227 cm²) is thearea of the electrode, ρ_(q) (=2.65 g/cm³) is the density of the quartz,and μ_(q) is the shear modulus of the quartz. Note that this equation isonly used for the frequency measurement in air to discount the effect ofthe density and viscosity of the solution.⁶

Ellipsometry Measurement

The thickness of the polymer brush film is measured by ellipsometryusing the Multiskop ellipsometer (Optrel GmbH, Germany) equipped with a632.8 nm laser. The measurement is done at 60° angle of incidence at dryand ambient conditions on Au substrate. At least three measurements areperformed at various spots of the film. The measured values of A and Ware used to simulate the thickness of the film using integratedspecialized software (Elli, Optrel) that is provided with theinstrument. The thickness of the polymer brush was calculated using amultilayer flat film model with an assumed refractive index of 1.5,which is typical for pNIPAM brush.⁷

Contact Angle Measurement

A static contact angle analysis of the electropolymerized film is doneusing a CAM 200 optical contact angle meter (KSV Instruments Ltd) withCAM 200 software. The measurement is achieved by making ˜1 μL drop ofMilli-Q water onto the film. At least three measurements are performedat various positions of the film.

Atomic Force Microscopy (AFM) Measurement

The AFM measurements are carried out in a piezo scanner from AgilentTechnologies. The scanning rate is between 0.8 to 1.0 lines/s.Commercially available tapping mode tips (TAP300, Silicon AFM Probes,Ted Pella, Inc.) are used on cantilevers with a resonance frequency inthe range of 290-410 kHz. The scanning of the electropolymerized film isperformed under ambient and dry conditions. All AFM topographic images(AAC tapping mode) are filtered, and analyzed by using SPIP software(Scanning Probe Image Processor, Imagemet.com) or Gwyddion 2.19software. The current sensing (CS) AFM analyses in contact mode weredone on the same set up using Pt-coated Si₃N₄ tip with radius around 20nm and force constant of 0.5 N/m. The measurements were done underambient conditions at 40-50% relative humidity and 20-25° C.temperature. All AFM topographic images (AAC tapping mode) are filtered,and analyzed by using SPIP software (Scanning Probe Image Processor,Imagemet.com) or Gwyddion 2.19 software.

X-ray Photoelectron Spectroscopy (XPS) Measurement

A PHI 5700 X-ray photoelectron spectrometer was equipped with amonochromatic Al Kα X-ray source (hn=1486.7 eV) incident at 90° relativeto the axis of a hemispherical energy analyzer. The spectrometer wasoperated both at high and low resolutions with pass energies of 23.5 eVand 187.85 eV, respectively, a photoelectron take off angle of 45° fromthe surface, and an analyzer spot diameter of 1.1 mm. All spectra werecollected at room temperature with a base pressure of 1×10⁻⁸ torr. Thepeaks were analyzed first by background subtraction using the Shirleyroutine. All the samples were completely dried in argon gas prior to XPSmeasurements.

Scanning Electron Microscopy

The morphology of the samples were examined by field emission scanningelectron microscopy (FE-SEM) using a JSM 6330F JEOL instrument operatingat 15 kV. Prior to SEM analysis, the films were thoroughly dried undervacuum for at least 24 hrs. SEM images were processed and analyzed usingImageJ software.

Attenuated Total Reflectance Fourier Transform Infrared (ATR-FTIR)

The ATR FTIR spectra were obtained on a Digilab FTS 7000 equipped with aHgCdTe detector from 4000 to 600 (cm-¹) wavenumbers. All spectra weretaken with a nominal spectral resolution of 4 cm⁻¹ in absorbance mode.All films were measured under ambient and dry conditions. The scanningof the film was done on ITO substrate for both patterned and unpatternedsurfaces.

REFERENCES FOR SYNTHESIS OF SECTION IV

The following references were cited in this section.

-   1 M. J. Felipe, R. Ponnapati, R. C. Advincula, Submitted to ACS    Appl. Mater. Interfaces.-   2 K. Matyjaszewski, P. J. Miller, N. Shukla, B. Immaraporn, A.    Gelman, B. B. Luokala, T. M. Siclovan, G. Kickelbick, T. Vallant, H.    Hoffmann, T. Pakula, Macromolecules 1999, 32, 8716.-   3 K. Yu, H. Wang, L. Xue, Y. Han, Langmuir 2007, 23, 1443.-   4 D. M. Jones, A. A. Brown, W. T. S. Huck, Langmuir 2002, 18, 1265.-   5 G. Sauerbrey, Z Phys. 1959, 155, 206.-   6 J. Bard, I. Rubinstein, Electroanalytical Chemistry, Vol. 22,    Marcel Dekker, Inc., New York, USA 2004, Ch. 1.-   7 a) N. C. Estillore, J. Y. Park, R. C. Advincula. Macromolecules    2010, 43, 6588. b) T. M. Fulghum, N. C. Estillore, C.-D. Vo, S. P.    Armes, R. C. Advincula. Macromolecules 2008, 41, 429.

While the invention described here specifically relates to the design,fabrication, characterization, and use of new types of electrodepositedpolymer coatings that offer both unique reversible wettability andelectro-optical properties, one of ordinary skills in the art, with thebenefit of this disclosure, would recognize the extension of this designto non-conducting polymers such as but not limited to acrylate, styrene,vinyl functional groups via cathodic, and other classes of materials.

All references cited herein are incorporated by reference. Although theinvention has been disclosed with reference to its preferredembodiments, from reading this description those of skill in the art mayappreciate changes and modification that may be made which do not departfrom the scope and spirit of the invention as described above andclaimed hereafter.

We claim:
 1. A composition comprising a substrate including a surfacehaving a coating formed thereon, where the surface comprises aconducting layer and where the coating comprises a non-fluorinatedconducting polymer or plurality of non-fluorinated conducting and/ornon-conducing polymers, where the coating has controllable redoxchemical, electrochromic and wettability properties.
 2. The compositionof claim 1, wherein the polymers comprise non-fluorinated conductingpre-grafted hydrophobic electropolymerizable monomers that areelectrodeposited by anodic electropolymerization or chemical oxidativepolymerization onto the conducting layer of the substrate.
 3. Thecomposition of claim 2, wherein the electropolymerizable monomerscomprise compounds of the general formula (I):A-RZ  (I) to form a non-fluorinated conducting polymer coating on theconducting layer to form a coated substrate, and where A is an anodicelectropolymerizable group and is 2,5-di(thiophen-2-yl)thiophen-3-yl, Ris an alkenyl group having between 1 and about 20 carbon atoms, whereone or more of the carbon atoms may be replaced by oxygen atoms, aminogroups, amide groups, ester groups, or mixtures thereof, and Z is an endgroup selected from the group consisting of COOH, COOR¹, and mixturesthereof, R¹ is a carbyl group having between 1 and about 10 carbon atomsand where the coating has controllable properties by applying anelectric potential across the coating, where the properties includeredox chemical, wettability and electrochromic or electro-opticalproperties.
 4. The composition of claim 3, wherein the compounds offormula are A_(p)-RZ.
 5. The composition of claim 3, wherein thecompounds of formula (I) are (A_(p))_(n)L-RZ.
 6. The composition ofclaim 1, wherein the polymers comprise non-fluorinated conductingpre-grafted hydrophobic electropolymerizable monomers that areelectrodeposited by cathodic electropolymerization or chemical reductivemethods which can involve radical or radical anion generation onto theconducting layer of the substrate.
 7. The composition of claim 1,wherein the coating further comprises one lower layer or a plurality oflower layers, each layer comprising one or a plurality of particles andwhere the layers deposited on conducting or electrode layer of thesubstrate surface influence a morphology of the electropolymerizedpolymers and where the layers are optionally removed to provide a opencoating structure.
 8. The composition of claim 7, wherein the polymerscomprise non-fluorinated conducting pre-grafted hydrophobic chains thatare electrodeposited by anodic electropolymerization onto the layers ofparticles.
 9. The composition of claim 8, wherein theelectropolymerizable monomers comprise compounds of the general formula(I):A-RZ  (I) to form a non-fluorinated conducting polymer coating on theconducting layer to form a coated substrate, and where A is an anodicelectropolymerizable group and is 2,5-di(thiophen-2-yl)thiophen-3-yl, Ris an alkenyl group having between 1 and about 20 carbon atoms, whereone or more of the carbon atoms may be replaced by oxygen atoms, aminogroups, amide groups, ester groups, or mixtures thereof, and Z is an endgroup selected from the group consisting of COOH, COOR¹, and mixturesthereof, R¹ is a carbyl group having between 1 and about 10 carbon atomsand where the coating has controllable properties by applying anelectric potential across the coating, where the properties includeredox chemical, wettability and electrochromic or electro-opticalproperties.
 10. The composition of claim 8, wherein the compounds offormula are A_(p)-RZ.
 11. The composition of claim 8, wherein thecompounds of formula (I) are (A_(p))_(n)L-RZ.
 12. The composition ofclaim 7, wherein the polymers comprise non-fluorinated conducting and/ornon-conducting pre-grafted hydrophobic chains that are electrodepositedby cathodic electropolymerization or chemical reductive polymerizationonto the conducting layer of the substrate.
 13. The composition of claim1, wherein the particles comprise polymer particles, polymer latexparticles, metal oxide particles, ceramic particles, salt particles,other conductive or non-conductive polymers or mixtures or combinationsthereof pre-assembled on the conducting layer of the substrate surface.14. The composition of claim 1, wherein the polymer particles comprisepolymer latex microsphere.
 15. The composition of claim 1, wherein theconducting layer comprises any suitable metal, metal alloy, metal oxide,polymer, and non-polymer surface, where the metal or metal alloyscomprise gold (Au), platinum (Pt), indium tin oxide (ITO), iridium (Ir),rhodium (Rh), iron (Fe), titanium (Ti), Zinc (Zn), aluminum (Al) andother metal, metal oxide, or metal alloy electrode and conductingelectrodes, mixtures or combinations thereof.
 16. The composition ofclaim 1, wherein the properties include superhydrophobicity andsuperlipophilicit, wherein the layers of the polymer particles provide asubmicron scaled roughness of a biomimetic surface imitating ageometrical microstructure of a surface of a biological system, andwherein the coatings exhibit tunable redox, electrochromic andwettability properties that are tuned by applying an electric potentialacross the surface.
 17. The composition of claim 1, wherein the coatingfurther comprises dopants, where the dopants permit control ofelectro-optical properties of the coating, where the properties arecontrolled by a level of doping and a nature of the polymers and layers.18. The composition of claim 1, wherein the coating further comprise asurfactant deposited on the coatings permitting further tuning of thewettability behavior of the coating.
 19. The composition of claim 1,comprises an anti-wetting composition, a filtration composition, ananti-corrosion composition, a de-icing composition, an anti-microbialcomposition, an electrochromic composition, or an electrophoreticcomposition or an electro-wetting composition.
 20. The composition ofclaim 1, wherein the polymers comprises non-fluorinated polythiophenepolymers having dual superhydrophobic and superoleophilic wettingproperties, which are easily and rapidly reversed with voltage orsurfactant coincident with electrochromism.